Environmental Engineering: Basic Principles 9783110468038, 9783110468014

Table of contents :
Preface
Contents
List of contributing authors
1. Introduction to environmental engineering
2. Ecology
3. Environmental Chemistry
4. Environmental microbiology
5. Environmental geology and hydrology
6. Transport phenomena in environmental engineering
7. Air pollution engineering
8. Water and wastewater treatment engineering
9. Soil treatment engineering
10. Modeling of environmental processes
11. Risk assessment
Index

Citation preview

Vesna Tomašić, Bruno Zelić (Eds.) Environmental Engineering

Also of Interest Industrial Biotechnology. Benvenuto, 2019 ISBN 978-3-11-053639-3, e-ISBN 978-3-11-053662-1

Green Chemistry and Technologies. Zhang, Gong, Bin (Eds.), 2018 ISBN 978-3-11-047861-7, e-ISBN 978-3-11-047931-7

Environmental Toxicology. Botana (Ed.), 2018 ISBN 978-3-11-044203-8, e-ISBN 978-3-11-044204-5

Physical Sciences Reviews. e-ISSN 2365-659X

Environmental Engineering Basic Principles

Edited by Vesna Tomašić and Bruno Zelić

Editors Prof. Vesna Tomašić University of Zagreb Faculty of Chemical Engineering & Technology Marulicev trg 19 10000 Zagreb Croatia [email protected] Prof. Bruno Zelić University of Zagreb Faculty of Chemical Engineering & Technology Marulicev trg 19 10000 Zagreb Croatia [email protected]

ISBN 978-3-11-046801-4 e-ISBN (PDF) 978-3-11-046803-8 e-ISBN (EPUB) 978-3-11-046807-6 Library of Congress Control Number: 2018949255 Bibliographic information published by the Deutsche Nationalbibliothek The Deutsche Nationalbibliothek lists this publication in the Deutsche Nationalbibliografie; detailed bibliographic data are available on the Internet at http://dnb.dnb.de. © 2018 Walter de Gruyter GmbH, Berlin/Boston Cover image: Fotosearch/Getty Images Plus Typesetting: Integra Software Services Pvt. Ltd. Printing and binding: CPI books GmbH, Leck www.degruyter.com

Preface Progress that was made in the last centuries, concerning human living conditions is more than evident. We live longer and better in a state of slight obsession where we always want more and more of new available products, food, accessorise, etc. that can make our lives more easy and comfortable. Somewhere in that rush of today’s lives we forgot or we rarely stop to think what the cost of such strong urbanisation and industrialization is. What is the cost of taking a new plastic bag in every store that we enter? Or throwing food and plastic in to the garbage without recycling? Or driving a car in the store that is 5 min away from our home? Or taking a 20 minutes shower every day with drinkable water? Besides the fact we stopped appreciating things due to their accessibility, what is the real cost of this and other everyday actions that we all do? Limited natural resources, polluted air and water, extinction of species, global warming, etc. are just some consequences of something that we love call modern life. But, how modern this destruction really is? How modern will be if tomorrows designers will have to focus on creating coolest gas masks because air will not be good for breathing without previous purification? Or creating a new canister that will be easy to transport from point A to point B because luxury of taking a shower in a bath will be just that – luxury? Since there is always but and since there is always hope, some things are changing. Slowly, but they still do and perhaps we can call them awareness awakening? Awareness that if we continue going in this direction one day we will run out of path and there will be nothing on horizon. Awareness that it is the final moment to put environment in to the focus. To change our selfish human perspective from us to nature. There is a saying “You can’t teach old dog new tricks” so perhaps the best way to start setting things right are new generations. To transfer the knowledge and information and sow the seeds of the awareness among engineering and science students hoping that one day that little seed will grow in to something strong and powerful. This textbook will, hopefully, be a good base or a good soil for that seed growth. It is organized in to eight different areas important to all present and future environmental engineers together with introduction, modelling of environmental processes and risk assessment. All that is necessary for new human direction when it comes to nature and putting her back in to the centre. The first chapter gives short introduction to basic environmental engineering principles and puts whole idea behind this new science field in to the concept. It presents the main areas of interest that are more deeply explored trough Chapters 2-9. The second chapter sets the stage with one of the basic aspects of environment – Ecology. Main focus of this field is to define diversity, distribution and number of particular organisms, as well as cooperation and competition between organisms, both within and among ecosystems. Basically, makes connections between organisms and their environment since it is not possible for one to work without the other. https://doi.org/10.1515/9783110468038-201

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Preface

In order to understand ecology, we have to understand the very base: environment and living organisms. Trough Chapters 3-5, entitled – Environmental Chemistry, Environmental Microbiology and Environmental Geology mentioned bases are covered. Chapter 3 presents the chemical nature of environmental problems and processes. Main focus is set on physical-chemical phenomena that occur in water, soil and atmosphere trying to summarize them on the basic environmental chemistry which is strictly related with chemical equilibrium phenomena. Because nothing in nature functions as a single but as a part of bigger picture, overcoming this principles a foundation for future construction of more complex environmental engineering problems is set, i.e. human impact on air, water and soil. Chapter 4 focuses on the dominant form of life on planet Earth – microorganisms. And although for many people they are out of sight and therefore out of mind almost every surface is colonized by them. From the environment point of view, environmental microbiology is concerned with the study of microorganisms in the soil, water and air and their application in bioremediation processes for biotreatment of water, wastewater, solid waste, soil and gas. And finally in Chapter 5 the importance of geological environment is presented since many natural hazards, which have great impact on humans and their environment, are caused by geological settings. On the other hand, human activities have great impact on the physical environment, especially in the last decades due to dramatic human population growth. Natural disasters often hit densely populated areas causing tremendous death toll and material damage. Demand for resources enhanced remarkably, as well as waste production. Exploitation of mineral resources deteriorates huge areas of land, produce enormous mine waste and pollute soil, water and air. Water, soil and air, their quality and protection are stressed down in Chapter 1 as most important issues in environmental engineering. Before exploring them more extensively in Chapters 7-9, Chapter 6 focuses on the engineering base of mentioned processes – transport phenomena. The main idea is to understand and then describe the specific process using phenomenological equations that rely on three elementary physical processes: momentum, energy and mass transport. In the end, if that is achieved those processes, using mathematical models (described in Chapter 10) can be predicted, designed, optimized, developed; some catastrophes can be avoided, multiple solutions for a certain problem can be presented, etc… Following the three main environmental issues, Chapter 7 focuses on air pollution. Air pollution is not just an environmental but a social problem which leads to a multitude of adverse effects on human health and standard of human life, state of the ecosystems and global change of climate. The chapter deals with the complexities of the air pollution and presents an overview of different technical processes and equipment for air pollution control, as well as basic principles of their work. As for air, Chapter 8 introduces water and wastewater characterization and gives an

Preface

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overview of the most important instrumental techniques used in water analysis. The presence of new pollutants (mostly of synthetic organic origin), the possibility of their characterization and modern removal techniques are particularly emphasized. The chapter describes the basic principles of biological water treatment, as well as modern processes involving membrane separation processes and advanced oxidation processes. The last issue, soil treatment is described in Chapter 9. As a conditionally renewable natural resource, soil has a decisive influence on sustainable development of global economy, especially on sustainable agriculture and environmental protection. In recent decades, a growing interest prevails for non-production soil functions, primarily those relating to environmental protection. It especially refers to protection of natural resources whose quality depends directly on soil and soil management. Soil contamination is correlated with the degree of industrialization and intensity of agrochemical usage and is one of the most dangerous forms of soil degradation with the consequences that are reflected in virtually the entire biosphere, primarily at heterotrophic organisms and also at mankind as a food consumer. As mentioned previously, by understanding chemical nature and transport phenomena together with microorganism behaviour many mentioned issues can be described, predicted, emerged problems, etc. can be solved by using mathematical models. In the Chapter 10 a short introduction into models (types of the models and their application) with accent on mathematical modelling in environmental engineering is given. Some basic advices on how to approach mathematical modelling, how to use different types of models and how to apply different methods for solving of mathematical models will be discussed on the examples describing the environmental processes. The final chapter, Chapter 11, introduces risk assessment and examines the basic concepts of risk and hazard, their causes, consequences and probabilities. The methodology of environmental risk assessment including effect assessment, exposure assessment and risk estimation/characterisation is overviewed. Some of the commonly used techniques in risk assessments are introduced and illustrated by examples Environmental risk assessment should provide input to the risk management so well-informed decisions can be made, to protect human health and the environment. Vesna Tomašić Bruno Zelić

Contents Preface

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List of contributing authors

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Anita Šalić and Bruno Zelić 1 Introduction to environmental engineering 1 1.1 A new engineering field? 1 1.2 New era – todays environmental engineering 2 1.3 Environmental issues 5 1.3.1 Air quality – Why it is such a problem? 8 1.3.2 Soil quality – What problems emerge from soil pollution? 1.3.3 Water quality – Are water wars our future? 11 1.4 What is the future of environmental engineering? 13 1.5 Conclusion 13 References 13 Ivančica Ternjej and Zlatko Mihaljević 2 Ecology 17 2.1 Introduction 17 2.2 Conditions for life 18 2.2.1 Abiotic factors 19 2.2.2 Biotic relationships 20 2.2.3 Community 27 2.2.4 Ecosystem 29 2.2.5 Succession 35 2.2.6 Biomes 37 2.2.7 Global changes 37 2.2.8 Applied ecology 39 References 41 Study questions 43 Tomislav Bolanča, Šime Ukić and Mirjana Novak Stankov 3 Environmental Chemistry 47 3.1 Introduction 47 3.2 Electrolytes and non-electrolytes 47 3.3 Concentration and activity 48 3.4 Ionization of water 49 3.5 Strong and weak acids 51 3.6 Strong and weak bases 55 3.7 Hydrolysis of salts 58

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3.8 3.9 3.10 3.11 3.11.1 3.11.2 3.11.3 3.11.4 3.11.5 3.11.6 3.12

Contents

Buffers 63 Reactions of complexation Redox reactions 68 Solubility of minerals 73 Nature of solvent and solute Temperature effect 75 Common-ion effect 75 Effect of complex formation Electrolyte effect 77 Effect of pH of the solution Solubility of gases 83 References 83

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74

76 78

Felicita Briški and Marija Vuković Domanovac 4 Environmental microbiology 85 4.1 Evolution of microorganisms 85 4.2 The microbial world: classification, metabolism and growth 86 4.3 Microbial diversity in the environment 97 4.4 Eutrophication process 105 4.5 Microorganisms in biodegradation and bioremediation 106 4.6 Biodegradation of organic pollutants 109 4.7 Principles of bioremediation 113 4.7.1 What is bioremediation? 113 4.7.2 Some groups of microbes 115 4.8 Composting 116 4.8.1 What is composting? Composting is nature’s way of recycling 116 References 118 A Appendix 120 Zoran Nakić, Marta Mileusnić, Krešimir Pavlić and Zoran Kovač 5 Environmental geology and hydrology 121 5.1 Floods as natural hazard 122 5.1.1 Hydrological cycle 123 5.1.2 Extreme events in hydrology 128 5.2 Groundwater as geological resource 131 5.2.1 Geological occurrence of groundwater 132 5.2.2 Water flow in unsaturated and saturated zone 133 5.2.3 Mass transport in porous medium 137 5.2.4 Modelling of water flow and solute transport in porous medium 140 5.2.5 Groundwater quality and pollution 143

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5.3 5.3.1 5.3.2 5.3.3 5.4

Impact of mining industry on environment and human health MineWaste 146 Impact on the environment 148 Impact on human health 151 Highlights 154 References 155 Questions 158

Aleksandra Sander, Jasna Prlić Kardum, Gordana Matijašić and Krunoslav Žižek 6 Transport phenomena in environmental engineering 159 6.1 Conservation laws 160 6.1.1 Macroscopic mass balance 160 6.1.2 Macroscopic energy balance 161 6.1.3 Macroscopic momentum balance 162 6.2 Motion of particles in fluid 163 6.3 Flow through porous media 167 6.4 Heat transfer 174 6.4.1 Heat conductivity 174 6.4.2 Heat transfer by conduction 175 6.4.3 Heat transfer by convection 176 6.4.4 Thermal radiation 178 6.5 Mass transfer 180 6.5.1 Molecular diffusion 181 6.5.2 Coefficient of mass diffusivity 181 6.5.3 Steady-state molecular diffusion in binary systems 182 6.5.4 Equimolar counter diffusion 183 6.5.5 Diffusion of component A through stagnant component B 183 6.5.6 Transient diffusion 183 6.5.7 Convective Mass Transfer 185 6.5.8 Interphase mass transfer 185 References 191 Examples for practice 191 Karolina Maduna and Vesna Tomašić 7 Air pollution engineering 195 7.1 Introduction 195 7.1.1 The complexities of the air pollution protection 195 7.1.2 Basic definitions and classifications 199 7.2 Transport and transformation of air pollutants in the atmosphere 207 7.2.1 Primary and secondary air pollutants 208

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7.2.2 7.2.3 7.2.4 7.3 7.3.1 7.3.2 7.3.3 7.3.4

Contents

Acid rain 214 Greenhouse effect 214 Global climate change vs global warming 215 Air pollution control 215 Selection of the air pollution control approach and control technique 215 Appropriate use of units and some basics of air pollution control 219 Control of particulate air pollution 222 Control of gaseous and vapor pollutants 233 References 238 Questions and exercises to get you thinking 240

Danijela Ašperger, Davor Dolar, Krešimir Košutić, Hrvoje Kušić, Ana Lončarić Božić and Marija Vuković Domanovac 8 Water and wastewater treatment engineering 241 8.1 Water and wastewater characterization and analysis 241 8.1.1 Biological characteristics 244 8.1.2 Physical characteristics 244 8.1.3 Chemical characteristics 245 8.2 Water and wastewater treatment by membrane processes 249 8.3 Biological wastewater treatment 256 8.3.1 Activated sludge process 258 8.3.2 Environmental factors 259 8.3.3 Membrane bioreactor 260 8.3.4 Biology of activated sludge 260 8.3.5 The Monod equation 262 8.4 Advanced oxidation processes 263 8.4.1 Chemical AOPs 264 8.4.2 Photo-assisted AOPs 268 8.4.3 Reactions and kinetics of hydroxyl radicals 271 References 273 Discussion, Questions and Exercises 275 Ivica Kisić, Željka Zgorelec and Aleksandra Percin 9 Soil treatment engineering 277 9.1 Introduction 277 9.2 Basics of soil science 278 9.3 Soil formation 280 9.3.1 Factors and processes of soil formation 9.3.2 Basic soil characteristics 281

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9.3.3 9.3.4 9.3.5 9.3.6

Roles of soil 294 Potential soil contaminants 297 Remediation technologies for contaminated soils 300 Types, forms, techniques and technologies of remediation References 311 Practical tasks 313 Study questions 315

Anita Šalić, Ana Jurinjak Tušek and Bruno Zelić 10 Modeling of environmental processes 317 10.1 Models 317 10.2 Mathematical models and modeling 319 10.3 Basic rules in mathematical modeling 323 10.4 Balance equations – Solving mathematical models 10.5 Conclusion 347 Important notification 348 References 348 Examples for practice 348 Hrvoje Kušić and Ana Lončarić Božić 11 Risk assessment 357 11.1 Introduction 357 11.1.1 What is risk? 357 11.1.2 What is hazard? 358 11.2 Looking for answers 359 11.3 Conceptual models 360 11.4 Risk assessment framework 362 11.5 Environmental risk assessment 364 11.6 Risk assessment methodology 366 11.7 Risk assessment for chemicals 368 11.8 Dose–response relationship 372 11.9 Risk assessment techniques 375 11.9.1 Risk matrices 375 11.9.2 Logic trees 377 11.9.3 Event trees 379 11.10 Conclusion marks 380 References 380 Study questions and tasks 382 Index

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List of contributing authors Danijela Ašperger University of Zagreb Faculty of Chemical Engineering and Technology Marulićev trg 19 HR-10000 Zagreb Croatia

Jasna Prlić Kardum University of Zagreb Faculty of Chemical Engineering and Technology Marulićev trg 19 HR-10000 Zagreb Croatia

Tomislav Bolanča University of Zagreb Faculty of Chemical Engineering and Technology Marulićev trg 19 HR-10000 Zagreb Croatia [email protected]

Ivica Kisić University of Zagreb Faculty of Agriculture Department of General Agronomy Svetošimunska cesta 25 HR-10000 Zagreb Croatia [email protected]

Felicita Briški University of Zagreb Faculty of Chemical Engineering and Technology Marulićev trg 19 HR-10000 Zagreb Croatia

Krešimir Košutić University of Zagreb Faculty of Chemical Engineering and Technology Marulićev trg 19 HR-10000 Zagreb Croatia [email protected]

Davor Dolar University of Zagreb Faculty of Chemical Engineering and Technology Marulićev trg 19 HR-10000 Zagreb Croatia

Zoran Kovač University of Zagreb Faculty of Mining, Geology and Petroleum Engineering Pierottijeva 6 HR-10000 Zagreb Croatia

Ana Jurinjak Tušek University of Zagreb Faculty of Food Technology and Biotechnology Pierottijeva 6 HR-10000 Zagreb Croatia

Hrvoje Kušić University of Zagreb Faculty of Chemical Engineering and Technology Marulićev trg 19 HR-10000 Zagreb Croatia [email protected]

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List of contributing authors

Ana Lončarić Božić University of Zagreb Faculty of Chemical Engineering and Technology Marulićev trg 19 HR-10000 Zagreb Croatia [email protected] Karolina Maduna University of Zagreb Faculty of Chemical Engineering and Technology Marulićev trg 19 HR-10000 Zagreb Croatia kmaduna@flkit.hr Gordana Matijašić University of Zagreb Faculty of Chemical Engineering and Technology Marulićev trg 19 HR-10000 Zagreb Croatia Zlatko Mihaljević University of Zagreb Department of Biochemistry and Molecular Biology Ante Kovačića 1 HR-10000 Zagreb Croatia [email protected] Marta Mileusnić University of Zagreb Faculty of Mining, Geology and Petroleum Engineering Pierottijeva 6 HR-10000 Zagreb Croatia Zoran Nakić University of Zagreb Faculty of Mining, Geology and Petroleum Engineering

Pierottijeva 6 HR-10000 Zagreb Croatia [email protected] Mirjana Novak Stankov University of Zagreb Faculty of Chemical Engineering and Technology Marulićev trg 19 HR-10000 Zagreb Croatia [email protected] Krešimir Pavlić University of Zagreb Faculty of Mining, Geology and Petroleum Engineering Pierottijeva 6 HR-10000 Zagreb Croatia Aleksandra Percin University of Zagreb Faculty of Agriculture Department of General Agronomy Svetošimunska cesta 25 HR-10000 Zagreb Croatia Anita Šalić University of Zagreb Faculty of Chemical Engineering and Technology Marulićev trg 19 HR-10000 Zagreb Croatia Aleksandra Sander University of Zagreb Faculty of Chemical Engineering and Technology Marulićev trg 19 HR-10000 Zagreb Croatia

List of contributing authors

Ivančica Ternjej University of Zagreb Department of Biochemistry and Molecular Biology Ante Kovačića 1 HR-10000 Zagreb Croatia [email protected] Šime Ukić University of Zagreb Faculty of Chemical Engineering and Technology Marulićev trg 19 HR-10000 Zagreb Croatia [email protected] Marija Vuković Domanovac University of Zagreb Faculty of Chemical Engineering and Technology

Marulićev trg 19 HR-10000 Zagreb Croatia mvukovic@flkit.hr Željka Zgorelec University of Zagreb Faculty of Agriculture Department of General Agronomy Svetošimunska cesta 25 HR-10000 Zagreb Croatia Krunoslav Žižek University of Zagreb Faculty of Chemical Engineering and Technology Marulićev trg 19 HR-10000 Zagreb Croatia [email protected]

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Anita Šalić and Bruno Zelić

1 Introduction to environmental engineering Abstract: Nowadays we can easily say that environmental engineering is truly an interdisciplinary science. Combining biology, ecology, geology, geography, mathematics, chemistry, agronomy, medicine, economy, etc. environmental engineering strives to use environmental understanding and advancements in technology to serve mankind by decreasing production of environmental hazards and the effects of those hazards already present in the soil, water, and air. Major activities of environmental engineer involve water supply, waste water and solid management, air and noise pollution control, environmental sustainability, environmental impact assessment, climate changes, etc. And all this with only one main goal – to prevent or reduce undesirable impacts of human activities on the environment. To ensure we all have tomorrow. Keywords: environment, engineering, pollution, environmental issues, humans “We won’t have a society if we destroy the environment” Margaret Mead

1.1 A new engineering field? The last two to three decades have confirmed a growing understanding that no part of our world is immune from environmental consequences of human activities. There is a pressing need for international cooperation and solidarity to preserve our forests, safekeeping our water and oceans, and stabilize the Earth’s atmosphere. The strong interest in protecting the environment has placed new responsibilities, especially for the engineers. Therefore, environmental engineers got under a huge spotlight. But the question is, Is this really a new concept? Did the humans of twentieth and twentyfirst centuries become more aware of their environment, protection of themselves, animals, plants, and plant populations from the effects of adverse environmental factors, including toxic chemicals and wastes, pathogenic bacteria and global effects such as warming, ozone layer depletion, and weather-pattern change? Or this goes way back in to the history? Although the first description of title “environmental engineer” appears somewhere around 1960s, the history of practice itself goes long in to the history. Since the early days of formation of the first communities (small group of people living on permanent settlements) a concern about clean water, waste separation, and sewage system had to be developed. With the growth of population, magnitude of those simple actions increased with addition of concern about air and soil quality.

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1 Introduction to environmental engineering

Scoping trough the written history of those early ages some examples of good environmental engineering practice can be found. Like Roman aqueducts that provided constant and clean water to the large cities of Empire or development of sewers system in some Indian cities 5,000 years ago. But true jump was made parallel with rapid industrialization in eighteenth century. With the increase of population in the cities, great migrations, increased exploitation of nature goods, increase demand for the large quantities of food and fresh water in one place, disposal of waste, appearance of massive epidemic of water transmitted diseases like cholera etc. all lead to significant concerned about public health. The first environmental engineer is said to have been Joseph Bazalgette who designed the first large-scale sewerage system in London in the mid-nineteenth century. This engineering venture is considered the beginning era of modern environmental engineering. Since then, the main idea – to improve natural environment for human habitation – remains the same but the amplitude of work severely intensified.

1.2 New era – todays environmental engineering Since the modern environmental engineering is relatively a new science maybe the best way to start is by defining it. Simply by scoping the Internet several definitions of environmental engineering can be found: The application of science and engineering knowledge and concepts to care for and/or restore our natural environment and/or solve environmental problems. (unknown) The application of science and engineering principles to improve the natural environment (air, water, and/or land resources) to provide healthy water, air, and land for human habitation (house or home) and for other organisms, and to remediate polluted sites. (unknown) The branch of engineering concerned with the application of scientific and engineering principles for protection of human populations from the effects of adverse environmental factors; protection of environments, both local and global, from potentially deleterious effects of natural and human activities; and improvement of environmental quality. (The American Academy of Environmental Engineers) Is that branch of engineering that is concerned with protecting the environment from the potentially deleterious effects of human activity, protecting human populations from the effects of adverse environmental actors and improving environmental quality for human health and wellbeing. (Peavy, 1985 [1]) Environmental engineering deals with design and construction of the processes and equipment intended to lessen the impact of man’s activities on the environment. (unknown)

Summarizes, the main goal of environmental engineering or better environmental engineers is to restore, to protect, to improve, and to provide. In order to do that, like any engineer they have to follow some basic principles like planning, design, construction and operation of equipment, systems, and structures for the benefit of society (Figure 1.1).

1.2 New era – todays environmental engineering

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Monitor Identify problem

Learn

Control

Evaluate

Organize

Figure 1.1: Basic principles for general problem management (inspired by [2]).

Develop plan

The basic step or better, one of the mayor responsibilities of environmental engineering is to monitor and potentially predict or even prevent harmful events in the environment. Using the previous knowledge environmental monitoring should ensures the management of natural resources contributing to sustainable development through processes and activities which characterize and monitor the quality of the environment. One of good examples is a strong pressure on upcoming industries to not only satisfy economic and technical sustainability principles but also social and ecological. Also there is a request for existing processes to adapt this new paradigm (Figure 1.2).

Air Pollution Engineering Soil Treatment Engineering Environmental Chemistry Mathematical modeling

Transport Phenomena Mass balances

Environmental Engineering

Environmental Microbiology Environmental Regulations Risk Assessment

Ecology

Environmental Geology Water Treatment Engineering

Figure 1.2: Suitability diagram.

According to Tonelli et al. [3] the need to reduce or contain the ecological footprint of the industry will affect the whole industrial system. In stepping to a low-carbon, resource-efficient approach, industry has to be considered not only as part of the problem but as part of the solution.

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1 Introduction to environmental engineering

Leading companies are preparing for this transformation on three fronts: rapidly reducing the resource- and energy-intensity in producing existing goods investigating the options for a thorough redesign of the industrial system radically rethinking business models.

Finally, a redesigned industrial system should – add the same value with a reduction of 25% on input materials and energy – make use of the 90% of discarded extracted materials – use benign materials that can be reused according to “cradle-to-cradle” concept – refurbish and reuse sophisticated long-lasting components – mimic and nurture the environmental niches. Let’s go back to the basic principles. Usually predictions and prevention are not possible and if a problem appears, then the cycle of the events is launched (Figure 1.1) in order to detect the presence of pollutants and tracking them back to their source. Usually, finding the source can present a significant challenge. For instance, the source of contamination in a lake could be anywhere within several thousands of acres of land surrounding the lake and its tributaries. Contamination of oceans can present even greater challenges in identifying the source. In order to, identify the problem, evaluate the situation, develop a plan and then potently resolve the situation requires extensive knowledge (Figure 1.3) of the chemistry and biology of the potential contaminants as well as the industrial or agricultural processes that might lead to their release (Chapters 2–6). And then, depending on area of pollution many other sciences get involved in finding a solution.

Social

Sustainable Environmental

Economical Figure 1.3: Diagram of environment engineering fundamentals.

This all means that a role of environmental engineer is also to coordinate other engineers to find best solutions for existing problems and to make rapid advancement in cleaning up the environment with eco-friendly techniques.

1.3 Environmental issues

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Usually many environmental problems cannot be stopped completely but rather reduced and during the process there are many ethical question involved. One of the most unpopular decisions that have to be made is to or not to shut down business that is a source of environmental pollutions because of the potential for severe economic consequences. That’s why; nowadays environmental engineers often work with businesses to determine ways to avoid or reduce the production of pollutants or to separate them so they can be disposed of in a safe manner (Chapter 11). At the end, one of the most valuable outcomes of the cycle (besides the protection and problem resolving) is obtained knowledge that can be utilized for future goals (Chapter 10). As examples for proposed system, air resource, solid waste and waste water management diagrams are presented in Figures 1.4–1.6.

1.3 Environmental issues The next important question is What are exactly environmental issues that today’s environmental engineer has to face? Usually they are divided in to three major groups: – air quality – soil quality – water quality and each of them present important part of the everyday life, not only for humans but for all other organisms on Planet – plants, microorganisms, animals, etc. Although it my seam that nowadays nature is rebelling more and more simply by watching number of catastrophes (tsunami in Indonesia, earthquakes in Italy, soil movement in South Amerika, etc.) it is still little percentage in total pollution amount in comparison to human impact. We can easily say that today there is serious environmental crisis due to global industrialization. Large quantities of water are polluted as well as air, forests are destroyed due to increased need for wood, land for food production or building new factories or simply urbanization, amount of solid waste is increasing rapidly with special accent on chemical and toxic material and chemicals, global warming, destruction of ozone layer are just some of the problems. Generally, factors impacting environment can be divided in two groups [4–6]: 1. Natural changes a. Natural processes b. Natural disasters 2.

Anthropogenic changes c.

Industrialization – although the industrialization is the base of human society development, in parallel it presents global environmental problem. Depletion of resources and creation of enormous waste is just some of the problems.

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Modelling Monitor Collect information

Air pollution Prevention source Liquid waste Solid waste

Identify problem

Learn

Control

Evaluate

Organize

Develop plan

Treatment

a)

1. Recovery techniques 2. Destruction techniques chemical waste gas treatment biological waste gas treatment

Modelling Monitor Collect informatin

Identify problem

Learn

Disposal or Control reuse

Evaluate

Wastewater collection

Transmision and pumping

b)

On-site * processing

Develop plan

Organize

Treatment*

Water pollution Prevention source

* 1. Screening 2. Plain sedimentation 3. Sedimentation with coagulation 4. Flocculation 5. Aeration 6. Disinfection 7. Softening

Modelling Monitor Collect informatin

Identify problem

Learn

Disposal or Control reuse

Processing and Recovery *

Evaluate

Organize

Develop plan

Transport

c)

Solid waste Prevention pollution source

On-site * processing

Solid waste storage and collection

*1. Material recoverey/recycling 2. Biological treatment 3. Energy recovery

Figure 1.4: Management systems for (a) air resource (b) water pollution and (c) solid waste pollution.

1.3 Environmental issues

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d. Change in ecological balance – topic that opens two important areas. First, wrong management of the biosphere leads to visible disturbance in ecosystem (mostly referring to extinction of wildlife and habitual destruction (i.e. destruction of rain forests or coral reefs)). Many species have extinct and many are almost there. Second problem is rapid genetic engineering development where genetically modified organisms can be harmful and even toxic to wildlife. e. Global warming – leads to rising temperatures of the ocean and earth surface. Year 2012 was characterized as the warmest year ever, after that year 2013 got the same title, as well as 2014, 2015, etc. As a consequence, polar ice caps are melting, sea level is rising flooding the area around sea where a great number of humane population lives which will lead to massive migration in the future etc. f. Overpopulation – is considered one of the most critical environmental problems. By year 2050, the global human population is expected to grow by 2 billion people, thereby reaching a level of 9.6 billion people. This will lead to major problem in water, food and energy supply. g. Natural resources depletion – is considered second crucial environmental problem. Since the starting of industrial era, the natural resources are constantly utilized for the production of one or more products for human consumption. One of the major natural resource that is being exploited rapidly are fossil fuels so in near future humans will have to think more about using renewable sources of energy. h. Deforestation – refers to clearing of green cover and making that land available for residential, industrial or commercial purpose. The process results in decreasing rainfall, increasing global temperature, loss of top soil, modification of climatic conditions, etc. i. Air pollution – release of different air pollutants in the atmosphere and environment causes many of other environmental issues like greenhouse effect, ozone layer destruction, smog formation, etc. j. Water pollution – it is believed that in near future water will be a rare commodity and that many economic and political problems will emerge from that since wars are expected for this natural resource. k. Waste disposal – as mentioned, rapid industrialization created large amounts of waste. Plastic, packaging, electronic waste, nuclear waste, etc. are becoming serious environmental problem. l. Some other issues: noise pollution, radiation pollution, soil erosion, climate change, ocean acidification, ozone layer depletion, acid rains, public health issues, etc. Unfortunately, all of these problems are global since they affect every individual, organization, community and country, and by becoming environmental stewards, it keeps the economy moving, which is necessary for growth and long-term viability and to solve them cooperation of all sectors is necessary.

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Since air, soil and water are defined as main areas of environmental engineering interest, few additional questions are addressed. 1.3.1 Air quality – Why it is such a problem? Air pollution may be defined as the presence in the atmosphere of any substance (or combination of substances) that is harmful to human health and welfare; offensive or objectionable to man, either externally or internally; or which by its presence will directly or indirectly adversely affect the welfare of man. It can be visible or invisible and perhaps the most familiar and obvious form of air pollution is smog hanging over cities. Air pollutants fall into two main categories: 1. those that are present in many areas because they are the products of daily-life activities such as transportation, power generation, space and water heating, and waste incineration, and 2. those generated by activities such as chemical, manufacturing, and agricultural processing whose pollutant byproducts tend to be localized in nearby areas or are spread long distances by tall stacks and prevailing winds. They are also categorized by their emission characteristics: 1. point sources, such as power plants, incinerators, and large processing plants; 2. area sources, such as space and water heating in buildings; and 3. mobile sources, mainly cars and trucks, but also lawn mowers and blowers and airplanes [7]. Besides these anthropogenic causes of air pollution, there are also natural sources like dust, methane, smoke and carbon monoxide from wildfires, volcano activity, etc. Air pollution presents a problem after exposer and depends on how pollutant is hazard. The most common sources of air pollution include particulates, ozone, nitrogen dioxide and sulphur dioxide. It can affect an individual, a certain groups or entire populations. It is a significant risk factor for a number of pollution-related diseases. Some of them are new cases of asthma, exacerbate (worsen) a previously existing respiratory illness, and provoke development or progression of chronic illnesses including lung cancer, chronic obstructive pulmonary disease, and emphysema. Air pollutants also negatively and significantly harm lung development, creating an additional risk factor for developing lung diseases later in life [8, 9]. Individual reactions to air pollutants depend on the type of pollutant a person is exposed to, the degree of exposure, and the individual’s health status and genetics [10]. Also the World Health Organization (WHO) estimated in 2014 that air pollution every year causes the premature death of some 7 million people worldwide [11]. India has the highest death rate due to air pollution. India also has more deaths from asthma than any other nation according to the WHO. In December 2013, air pollution was

1.3 Environmental issues

9

estimated to kill 500,000 people in China each year. There is a positive correlation between pneumonia-related deaths and air pollution from motor vehicle emissions. Besides humans, air pollution effects agriculture. Yield reductions on a national scale were estimated to be about 5% in USA, with the economic benefit of reducing ozone concentrations by 40% estimated to be about 3 billion dollars annually. The ozone exposure corresponding to a 10% yield loss is exceeded over most of Europe, indicating the large potential for substantial effects on crop production. Detailed continent wide estimates of actual production losses have not yet been made, although individual filtration studies at Mediterranean sites, where ozone exposures are among the highest in Europe, have shown yield losses above 20% on sensitive crops. Situation is even more critical in developing countries like valley of Mexico – 40% yield lost in sensitive cultivar, Nile delta – 30%, Pakistan – 40%, etc. [12] Also, by each year economy costs are increasing. According to the calculations, global air pollution-related healthcare costs are projected to increase from USD 21 billion (using constant 2010 USD and PPP exchange rates) in 2015 to USD 176 billion 2005 in 2060. By 2060, the annual number of lost working days, which affect labour productivity, are projected to reach 3.7 billion (currently around 1.2 billion) at the global level. And the annual global welfare costs associated with the premature deaths from outdoor air pollution are projected to rise from USD 3 trillion in 2015 to USD 18–25 trillion in 2060 [13]. Besides those impacts air pollution is directly connected with smog, acid rains, eutrophication, depletion of ozone layer and global warming. So, if air pollution is present are there solutions for it? Some of them are 1. use public mode of transportation, walk, drive bike or carpool 2. conserve energy 3. understand the concept of Reduce, Reuse and Recycle 4. emphasis on clean energy resources 5. use energy efficient devices 6. use hybrid cars 7. utilize alternative fuels. For more details about air pollution environmental engineering see Chapter 7. 1.3.2 Soil quality – What problems emerge from soil pollution? Soil contamination is mainly located close to waste landfills, industrial/commercial activities diffusing heavy metals, oil industry, military camps, and nuclear power plants. As European society has grown wealthier, it has created more and more rubbish. Each year in the EU, 3 billion tonnes of solid wastes are thrown away (some 90 million tonnes of them are hazardous). This amounts to about 6 tonnes of solid waste for every man, woman and child [14, 15]. In the US, the army alone has

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estimated that over 1.2 million tonnes of soils have been contaminated with explosives, and the impact of explosives contamination in other countries in the world is of similar magnitude [16]. Based just on mentioned numbers it is obvious that soil pollution probably represents the most faced problem in environmental pollution. Generally, it is because 1. Soil is a point of concentration and recovery of toxic compounds, chemicals, salts, radioactive materials or disease causing agents, which have adverse effects on plant growth and animal health. 2. Soil pollutants can contaminate water: water infiltration is the movement of water from the soil surface into the soil profile and soil is a valuable resource that support cultures and plant life. 3. Soil pollutants have an adverse effect on the physical, chemical and biological properties of the soil and reduce its productivity. Main causes of soil pollution are as follows 1. industrial activity, especially since the amount of mining and manufacturing has increased; 2. agricultural activities, pesticides and fertilizers which are full of chemicals that are not fully degradable in nature and are widely utilized around the world; 3. waste disposal, where there is also a large amount of industrial and municipal waste that is dumped directly into landfills without any treatment and 4. accidental oil spills, where oil leaks can happen during storage and transport of chemicals [17]. As a historical example, serious problem was caused by widespread application of the pesticide DDT to control agricultural pests in the years following World War II. It was used in urban aerial sprays to control urban mosquito, gypsy moth, Japanese beetle and other insects in the 1940s. While the agricultural benefits were outstanding and crop yields increased dramatically thus reducing world hunger substantially, and malaria was controlled better than it ever had been, numerous species were brought to the verge of extinction due to the impact of the DDT on their reproductive cycles. By 1972, DDT was banned from the United States due to widespread development of resistance to DDT and evidence that DDT use was increasing preterm births and also harming the environment [18]. DDT was found to cause behavioural anomalies and eggshell thinning in populations of bald eagles and peregrine falcons. So back to the question from title, What problems emerge from soil pollution? Main effects of soil pollution are 1. effect on health of humans 2. effect on growth of plants 3. decreased soil fertility 4. toxic dust.

1.3 Environmental issues

11

Contaminated or polluted soil directly affects human health through direct contact with soil or via inhalation of soil contaminants which have vaporized. The implication of soils to human health is direct such as ingestion, inhalation, skin contact and dermal absorption. Some epidemiological examples include geohelminth infection and potentially harmful elements via soil ingestion, cancers caused by the inhalation of fibrous minerals, hookworm disease and podoconiosis caused by skin contact with soils [19]. Elliott et al. [20] have found small excess risks of congenital anomalies and low and very low birth weights in populations living near landfill sites. Different contaminants have different effects on human health and the environment depending on their properties. The contaminant effect depends on its potential for dispersion, solubility in water or fat, bioavailability, carcinogenicity and so forth [15]. Not unexpectedly, soil contaminants can also have significant deleterious consequences for ecosystems [21]. An example is already mentioned DDT pesticide. Soil contaminates can alter metabolism of some microorganisms resulting in eradication of some of the primary food chain, which in turn could have major consequences for predator or consumer species. Negative effect is also present in plant metabolism. Result is often reduced crop yields. This has a secondary effect upon soil conservation, since the languishing crops cannot shield the Earth’s soil from erosion. As for air pollution, there are some clean-up options to reduce already made mess. Most of them are based on remediation strategies: 1. excavate soil and take it to a disposal site 2. aeration of soils at the contaminated site (enhances the risk of creating air pollution) 3. thermal remediation 4. bioremediation 5. extraction of groundwater or soil vapour with an active electromechanical system 6. containment of the soil contaminants (such as by capping or paving over in place) 7. phytoremediation, or using plants (such as willow) to extract heavy metals 8. mycoremediation, or using fungus to metabolize contaminants and accumulate heavy metals and 9. remediation of oil contaminated sediments with self-collapsing air microbubbles [22]. For more details about soil treatment environmental engineering see Chapter 9. 1.3.3 Water quality – Are water wars our future? Water occupies two-third of Earth’s surface and that makes it not only a valuable resource for humans but entire ecosystem. By the growth of human population it will be utilized in more and more activates associated with humans. That will

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undoubtedly lead to reduction of overall water quality and poorer water quality usually means water pollution. Besides that, water pollution can be defined in many ways. Usually, it means one or more substances have built up in water to such an extent that they cause problems for animals or people. Factors that contribute to water pollution can be categorized into two different groups: 1. Point sources that are the easiest to identify and control. Some of sources are factories, sewage system, power plants, underground coalmines, oil wells, etc. 2. Non-point sources are ambiguously defined and harder to control. Some of the sources are: – when rain or snow moves through the ground and picks up pollutants as it moves towards a major body of water, – the runoff of fertilizers from farm animals and crop land, – air pollutants getting washed or deposited to earth and – storm water drainage from lawns, parking lots, and streets [23, 24]. Regardless the source, in the last decades it became more then obvious that water is becoming a serious environmental problem. Due to environmental impact, drought and flooding are present in many parts of the world. Both of these events strongly impact food supplies and economy. On the other hand, being a universal solvent, water is a major source of infection. According to WHO 80% diseases are water borne. Infectious diseases, like cholera, typhoid fever and other diseases gastroenteritis, diarrhoea, vomiting, skin and kidney problem are just some of them [25]. Drinking water in various countries does not meet WHO standards. Water pollution causes approximately 14,000 deaths per day, mostly due to contamination of drinking water by untreated sewage in developing countries [26]. Not only humans but, as mentioned, entire biosystem is affected by water pollution. Biomass and diversity of communities are to be effected when large amount of toxic materials are released into the streams, lakes and coastal waters in the ocean. This waste can increase secondary productivity while altering the character of the aquatic community. Most fishes especially the species desired as food by man are among the sensitive species that disappear with the least intense pollution. Direct damage to plants and animals nutrition also affects human health. Plants nutrients including nitrogen, phosphorus and other substances that support the growth of aquatic plant life could be in excess causing algal bloom and excessive weed growth. This makes water to have odour, taste and sometimes colour. Ultimately, the ecological balance of water is altered [26]. Additionally, approximately 97.5% of all water is either salt water or water that has become polluted. Of the remaining 2.5%, nearly 70% is frozen in glaciers and the polar ice caps. Less than 0.01% of all water worldwide is available for human use in lakes, rivers, reservoirs and easily accessible aquifers. Combining all of this with all

References

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that is mentioned previously and the fact that conflicts over water, both within countries and between countries, are sharply increasing human future is becoming slightly shaken. Fortunately, up to now few of these conflicts have led to violence [27]. But who knows what will happen tomorrow. For more details about water and waste water treatment engineering see Chapter 8.

1.4 What is the future of environmental engineering? It is said that environmental engineering has a proud history and a bright future. It is a career that may be challenging, enjoyable, personally satisfying and monetarily rewarding [28]. Predictions are that employment of environmental engineers will grow by 15% from 2012 to 2022, which is faster than the average for all occupations. If we think beyond 2022 and further in to the future, it is expected that technology development will continue growing bringing new challenges for the environment. Population will also grow which will enhance the need for resources, food and water supplies, cities will get overpopulated, etc. Also, “going green” move became more and more popular so new approaches to develop new “green” methods will be needed. Accent on prevention rather than controlling will be the main stream of the future. A new even more dangerous contaminates will probably emerge. A climate change will become more and more obvious. All of this and more in the end will need proper coordination and management to avoid pollution or eco-damage. And this is where environmental engineering will build bright and prospers future.

1.5 Conclusion At the end of this first chapter we can just hope that we managed to awaken interest for this broad field. Field, which will rapidly change with development of human society. One can just hope that it will keep the step, walk shoulder to shoulder one next to another, otherwise, if it stutters a little it will have deep consequences on environment and society. Also, following chapters of this book will give wider picture of problems environmental engineering is facing and hopefully give enough tools to fight all challenges that the future is bringing.

References [1] [2]

Peavy HS, Rowe DR, Tchobanoglous G. Environmental engineering. UK: McGraw-Hill; 1985. Osgood N. 1.040 project management. Cambridge, USA: Massachusetts Institute of Technology: MIT OpenCourseWare, 2004 Spring. https://ocw.mit.edu. License: Creative Commons BY-NC-SA.

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[5] [6] [7] [8] [9] [10] [11]

[12] [13] [14] [15]

[16] [17] [18]

[19] [20] [21]

[22] [23] [24] [25]

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Tonelli F, Evans S, Taticchi P. Industrial sustainability: challenges, perspectives, actions. Int J Business Innovation Res. 2013;7:143–63. Pereira JC. Environmental issues and international relations, a new global (dis)order – the role of international relations in promoting a concerted international system. Rev Bras Polít Int. 2015;58:191–209. Salati E, Dos Santos AA, Klanin I. Relevant environmental issues. Estudios Advancados. 2007;21:107–27. Anand SV. Global environmental issues. Sci Rep – UK. 2013;2:632–40. Pfafflin JR, Ziegler EN. Encyclopaedia of environmental science and engineering, Volume 1 A-L. Boca Raton, Florida: CRC Press Taylor & Francis Group 2006. Laumbach RJ, Kipen HM. Respiratory health effects of air pollution: update on biomass smoke and traffic pollution. J Allergy Clin Immunol. 2012;129:3–13. Del Donno M, Verdur A, Olivieri D. Air pollution and reversible chronic respiratory diseases. Monaldi Arch Chest Dis. 2002;57:164–66. Vallero DA. Fundamentals of air pollution. USA: Elsevier Academic Press; 2014. WHO, 7 million premature deaths annually linked to air pollution”. New relies, 25 March 2014. (http://www.who.int/mediacentre/news/releases/2014/air-pollution/en/) Accessed 1 January 2018. Marshal F, Ashmore M, Hinchcliffe F. A hidden threat to food production: air pollution and agriculture in the developing world, GATEKEEPER SERIES No. 73 Policy highlights: The economic consequences of outdoor air pollution. OECD better policies for better lives. Paris, France: OECD, 1–20. Eurostat, Environmental data centre on waste, (http://epp.eurostat.ec.europa.eu/portal/ page/portal/waste/introduction) Accessed 1. January 2018. Panagos P, Van Liedekerke M, Yigini Y, Montanarella L. Contaminated sites in Europe: review of the current situation based on data collected through a European network. J Environ Public Health. 2013;2013:1–11. Lewis TA, Newcombe DA, Crawford RL. Bioremediation of soils contaminated with explosives. J Environ Manage. 2004;70:291–307. Ranieri E, Bombardelli F, Gikas P, Chiaia B. Soil pollution prevention and remediation. Appl Environ Soil Sci. 2016;2016:1–2. Shabbira A, DiStasioa S, Zhaob J, Cardozob CP, Wolff MS, Caplana AJ. Differential effects of the organochlorine pesticide DDT and its metabolite p,pV-DDE on p-glycoprotein activity and expression. Toxicol Appl Pharmacol. 2005;203:91–98. Abrahams PW. Soils: their implications to human health. Sci Total Environ. 2002;291:1–32. Elliott P, Briggs D, Morris S, De Hoogh C, Hurt C, Kold Jensen T, et al. Risk of adverse birth outcomes in populations living near landfill sites. Bmj. 2001;323:363–68. Hogan M, Patmore L, Latshaw G, Seidman H. Computer modelling of pesticide transport in soil for five instrumented watersheds, prepared for the U.S. Environmental Protection Agency Southeast Water laboratory. Ga A, edited by. Sunnyvale, California: ESL Inc.; 1973. Agarwal A, Zhou Y, Liu Y. Remediation of oil contaminated sand with self-collapsing air microbubbles. Environ Sci Pollut Res Int. 2016;23:23876–83. Moss B. Water pollution by agriculture. Phil Trans Royal Society B. 2008;363:659–66. Hogan CM. Water pollution. Encyclopedia of earth. Washington, DC: National Council on Science and the Environment; 2010. Juneja T, Chauhdary A. Assessment of water quality and its effect on the health of residents of Jhunjhunu district, Rajasthan: a cross sectional study. J Public Health Epidemiol. 2013;5: 186–91.

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[26] Owa FD. Water pollution: sources, effects, control and management. Mediterr J Soc Sci. 2013;4:65–68. [27] Levy BS, Sidel VW. Water rights and water fights: preventing and resolving conflicts before they boil over. Am J Public Health. 2011;101:778–80. [28] Weiner R, Matthews RA. Environmental engineering. 4th ed. USA: Elsevier Science; 2003.

Ivančica Ternjej and Zlatko Mihaljević

2 Ecology Abstract: Ecology is a science that studies the mutual interactions between organisms and their environment. The fundamental subject of interest in ecology is the individual. Topics of interest to ecologists include the diversity, distribution and number of particular organisms, as well as cooperation and competition between organisms, both within and among ecosystems. Today, ecology is a multidisciplinary science. This is particularly true when the subject of interest is the ecosystem or biosphere, which requires the knowledge and input of biologists, chemists, physicists, geologists, geographists, climatologists, hydrologists and many other experts. Ecology is applied in a science of restoration, repairing disturbed sites through human intervention, in natural resource management, and in environmental impact assessments. Keywords: elements of ecology, environment, habitat, biodiversity

2.1 Introduction The phrase ecology is used often today and has a wide meaning. Ecology is referred to as a science, ecology as nature, ecology as an idea and ecology as a movement. In this chapter, ecology is used to refer to ecology as a science that studies the mutual interactions between organisms and their environment. For practical reasons, ecology is typically divided into plant ecology, animal ecology and human ecology. One of the first to describe the significance of ecological observations was renowned natural historian Charles Darwin, in his book On the Origin of the Species [1]. Darwin explained numerous examples of evolution (adaptation, natural selection, fighting for survival and extinction of the species) which included an entire range of mutual relations between organisms and their interactions with the conditions of their environment. The word ecology (Greek: oikos = house, home, habitat; logos = study of, knowledge) was first coined by the German biologist Ernst Haeckel in his book Generelle Morphologie der Organismen [2]. The fundamental subject of interest in ecology is the individual, the plant or animal organism. Individuals of plants or animals do not live isolated, but are typically grouped, and such groups of similar individuals are called species. Though biologists

This article has previously been published in the journal Physical Sciences Reviews. Please cite as: Ternjej, I., Mihaljevic, Z. Ecology. Physical Sciences Reviews [Online] 2017, 2 (10). DOI: 10.1515/psr2016-0116 https://doi.org/10.1515/9783110468038-002

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have not agreed on a single definition of the species, most accept that species are groups of individuals that share similar morphological and genetic traits, and individuals of a species are able to reproduce with one another and create fertile offspring. Today, ecology is a multidisciplinary science: in order to provide answers to many of the questions this field of science deals with, cooperation is needed from many different fields. This is particularly true when the subject of interest is the ecosystem or biosphere, which requires the knowledge and input of biologist, chemists, physicists, geologists, geographists, climatologists, hydrologists and many other experts. Humans, in addition to consuming massive amounts of energy, have polluted nature with industrial waste, harmful gases, pesticides, heavy metals and organic compounds, thereby drastically reducing the diversity of plant and animal species, which has started to change the ecological balance. The altered environment negatively impacts human health and is even gradually threatening human survival (climate change, greenhouse effect, destruction of the Earth’s ozone layer). Industry – the foundation for global prosperity – has created significant global threats to humankind’s opportunities for continued survival. Therefore, future development should be based on protecting the environment, in the form of sustainable development and management. This implies that the use of natural resources must be tolerable, allowing those resources to regenerate and remain in ecological balance. If we master the fundamental principles of ecology, we will be more easily able to create the conditions for the rational use of natural resources of the biosphere, and to improve relations between humans and their natural environment.

2.2 Conditions for life Many factors influence the distribution and survival of species. Generally, they can be divided into factors of the non-living environment – abiotic – and factors of the living environment – biotic factors. The habitat, or biotope, as the area where a given species lives, is characterised by a specific complex set of ecological factors. None of these factors acts alone, and so organisms are distributed only in those areas where the gradients of specific factors in play overlap in a suitable way. The range of fluctuation of a single ecological factor, within which the life of a certain organism is possible, is called ecological valence (Shelford’s law of tolerance) (Figure 2.1). However, the effect of one ecological factor may not be within the limits of the ecological valence, and organism could not survive. For each ecological factor, there is an optimal range, and a minimum and maximum. At both the minimum and maximum, the intensity of ecological factor corresponds to the stress zone, or area pessimum (from lat. pessimus – very bad). Optimum is that quantity or intensity of the ecological factor whose intensity is most suitable for the organism and the consequence is his maximal growth and development. The concept of the limiting effect of an ecological factor was introduced in ecology by V. E. Shelford [3], and it is valid for all ecological factors and for all organisms.

2.2 Conditions for life

19

upper limit of tolerance

lower limit of tolerance

species absent

low population

low

low

area of greatest abudance

Zone of physiological stress

population

high

range of optimum Zone of intolerance

Zone of physiological stress

low population gradient

Zone of intolerance

species absent high

Figure 2.1: A schematic representation of the ecological valence [inspired by [4].

Organisms with a wide range of tolerance for an ecological factor are called eurivalent species, while organisms with a narrow range of tolerance for an ecological factor are called stenovalent species. What is interesting is that one single life factor at a minimum can exclude a certain species from a given habitat, regardless of the fact that all other factors may be at optimum ranges. 2.2.1 Abiotic factors Temperature and moisture are key ecological factors that determine the distribution and development of plants, and based on these factors, we can differentiate different vegetation zones on Earth. For animals, vegetation is an important factor as shelter and a source of food. In areas where ecological conditions are unfavourable, and the plant cover is poorly developed, the diversity and abundance of animals is also lower, due to the scarcity of suitable shelters and available food. Many animals are distributed only with certain temperature limits that are suitable for their survival, and the very distribution of climate areas on Earth becomes a barrier to their broader dispersal. Monkeys and parrots are primarily distributed in the tropical and subtropical zones; the polar bear, walrus and some diving birds are distributed in the polar regions. Another important ecological factor is light. The rhythmic change of light is a dependent factor for many of the daily and seasonal phenomena and activities in plants and animals. Day length is a factor that determines when leaves begin to fall in many deciduous tree species in moderate climate zones. There are long- and short-day organisms. For example, barley is a long-day plant and blooms under long-day light, while in tobacco, long days prevent blooming. Constant daylight is a reason why plants in the tropics bloom year round, and why polar plants fail to thrive in other parts of the world, as they are adapted for

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long days. Trout spawns at a temperature of 6 – 7 °C (winter), though spawning can be achieved experimentally in periods of higher temperature (summer) just by reducing the amount of daylight. Shortening daylight also stimulates migrating birds to fly south. How organisms react to the rhythmic changes in the intensity of light – day, night – is of particular ecological importance. Among mammals in temperate forests 30–40 % are active during the day and 60–70 % are active during the night. The distribution of animals also depends on light. For example, in Norway, the wood mouse (Apodemus sylvaticus) reaches the maximum latitude of 62°N. The reason for this is the duration of the summer nights, which in that part of the world lasts only 5 hours. Since the wood mouse is a nocturnal animal (active and feeds at night), a shorter night is one of the main reasons why this animal cannot disperse further north, as during such short nights, this animal simply cannot feed enough to ensure its survival. Specific behaviour patterns are also tied to changes in photoperiod and temperature, such as bird migrations. In aquatic ecosystems, primary producers (phytoplankton, macrophytes and sea grasses) are limited to the depth of light penetration, water temperature and the quantity of available nutrients, while for animals, the quantity of metabolic gases (oxygen and carbon dioxide), salinity and pressure (in the sea) are important factors. 2.2.2 Biotic relationships Population The living area of a species consists of a multitude of intertwining abiotic factors that affect the organism. However, organisms of the same species, and those of other species, also come into contact and affect one another. A population is a group of individuals of the same species in a given area. Each population has their own dynamics and properties: a size of the population, spatial distribution, age structure, sex ratio, birth, death, immigration and emigration rates. The spatial distribution of individuals in the environment could be caused by the distribution of resources or by social relationships among the individuals. Mutual interactions and relationships between individuals of the same species are called intraspecific relations. If a certain resource essential for the life of the population is limited, this will result in competition among the population members (intraspecific competition), which can limit the population size. When ecologists investigate endangered species, the size of the surviving population is of crucial importance in the design of proper management. Population size also depends on other population characteristics: natality, mortality, survivorship, reproduction potential and dispersion. Populations are increased through the birth of new individuals (natality) and the arrival of new individuals (immigration), while they are reduced through death (mortality) and those leaving the population (emigration).

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21

Population growth can be exponential or logistic. Exponential population growth is characteristic in invertebrates and some vertebrates (rodents) while colonising new habitats, when the two most important resources – space and food – are not yet limiting (Figure 2.2). But no real population can for long continue increasing exponentially and are instead stabilised at a certain level.

Number of individuals

1,000

800

600

400

200

0

Time

Figure 2.2: The exponential growth curve [inspired by [5].

Logistic growth is caused by the limitation of resources in the habitat. It is characterised by the carrying capacity (K) of the environment, which indicates the maximum population size that the habitat can support with its resources. For example, sheep brought to the Australian island of Tasmania in 1800 experienced a rapid population expansion to almost two million individuals. The result was massive competition for food and by 1885, their numbers had declined and stabilised, to the level of about 1.6 million individuals (Figure 2.3). The terms r-selection and K-selection have been used by ecologists to describe the growth and reproductive strategies of various organisms. The r and K classification was originally proposed by R. McArthur and O.E. Wilson [6]. R-selected species live in variable, unstable habitats, while K-selected species reside in stable environments. Small body size, early reproductive maturity, high fecundity and low parental

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2.0 Number of individuals (in milions)

carrying capacity (k)

1.5

1.0

5

1800

1825

1850

1875

1900

1925

Year

Figure 2.3: The logistic growth curve. When the carrying capacity is reached, there is no further increase in density [inspired by [5].

investment are main characteristics of the r-selection species. Flies and most invertebrates are an example of an r-selected species. The extreme opposite is K-selection species with low fecundity and high parental investment. Most mammals are examples of K-selected species. 2.2.2.1 Interspecific relationships Relationships between different species (populations) are called interspecific relationships and imply an entire series of mutual influences, such as competition, predation, parasitism, mutualism and commensalism. For example, one species may feed on another, and is, therefore, dependent on it. Competition Species can compete for the same food source or space, and thus they are in competition. An interesting example is the barnacles Chthalamus stellatus and Balanus balanoides. Both species inhabit the tidal zone, though Chthalamus always is found in higher areas and Balanus in lower areas of that zone. Connell [7] conducted experiments with these barnacles: he moved the rocks housing Chthalamus to lower areas and those housing Balanus to higher areas, and he physically removed the Balanus from the rocks in the lower areas and Chthalamus from the rocks in the higher areas. Connell found that Chthalamus was able to survive normally in the lower level on the rocks he had placed there. However, Balanus did not fare well on the rocks in the higher zone, as this species is less tolerant to drying out. It is interesting that Connell also took photographs of larvae of both species equally

2.2 Conditions for life

23

colonising the lower zone. However, as Balanus individuals grow, their base expands more rapidly and they literally expel the Chthalamus larvae from the rocks. On the one hand, the ecological factors act on the vertical distribution of these species; while on the other hand, during colonisation of rocks the acting factor is competition. Competition can be so great that one species completely expels another from a habitat. This is called competitive exclusion. Many allochthonous (alien) species can also expel autochthonous (indigenous) species through this process of competitive exclusion. In many clean rivers still in a relatively natural state, the introduction of rainbow trout (Oncorhynchus mykiss) has resulted in significant reductions of populations of the native brook trout (Salmo trutta). The introduction of alien and invasive species has particularly impacted the Dinaric karst rivers of the Adriatic basin, which abound in endemic species [8]. Another example is the introduction of the American grey squirrel (Sciurus carolinensis) in Great Britain between 1876 and continued to 1915 or later. By the mid-1920s, the population of the native red squirrel (Sciurus vulgaris) had declined drastically due to disease. The spread of introduced species cooccurred with the declining population of the indigenous species. It has been confirmed that the grey squirrel spread in those habitats not inhabited by the domestic red squirrel, and also into those where the domestic squirrel population was in decline due to disease. The introduced species was stronger in competition for food sources and habitat, and also more resistant to disease, and therefore drove out the native species in a great part of Britain. The domestic red squirrel has maintained large populations only in certain isolated localities, which had not been exposed to the epidemic (e. g. on the Isle of Wight off the south-east coast of Great Britain) [9]. There are countless examples of competition. However, most species having the same needs often share the same habitat. This is considered coexistence, indicating that they have somehow succeeded in overcoming or reducing the competition between them. One way different species use the resource is to use it at different times. In forests, predator bird species, such as falcons and buzzards, hunt by day, while owls hunt by night. Both groups feed on small mammals. The macrozooplankton of Visovac Lake in Krka National Park (Croatia) consists of four species of water fleas. Of these, two species are in direct competition for food, and both belong to the same order of water fleas (Daphnia) [10]. The species Daphnia longispina is small and feeds primarily on algae from 15–20 μm in size. The second water flea species, Daphnia cucullata, feeds on green algae of the same size. However, unlike the first species, this species can also feed on slightly larger amounts of small organic particles. The annual cycle of these two crustacean species is shown in Figure 2.4. In this case, the spatial and temporal distribution of these species is primarily determined by food sources. It can be noted that D. cucullata develops the densest populations in June, when the species D. longispina is not present yet in the macrozooplankton. Namely, this species begins to appear in July, and when it does, it slowly forces out the first species. During July, their populations are separated spatially: D. cucullata is found at depths of 10 and 20 m, while D. longispina is

Number of individuals / L

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2 Ecology

40

III II

30

I XII

20

XI X IX

10 VIII

Month

VII VI

1 5

depth (m)

V

10 15 20

IV

D.cucullata

D.longispina

Figure 2.4: Niche separation in space and time between two Daphnia species in Visovac Lake.

found at depths of 5 and 15 m. However, for the remainder of the year, only D. longispina is present in the macrozooplankton. As explained in these examples, different species can coexist by separating their ecological niches, either spatially or temporally. Most often, the term ecological niche implies the position of a species in the community in terms of food, which can be considered its microhabitat. It could be said that the habitat of a species is its “address,” while its niche is its “profession”! In that way, species living at the same “address” need not have the same “profession.” However, this understanding of the ecological niche has been gradually evolving over the past 30 years. Today, many biologists feel that the ecological niche is not determined only by the feeding methods, but also by all the other ecological factors to which a species has adapted. There is yet another way to avoid competition. In Asia Minor, the distribution ranges of two passerine bird species overlap: the western rock nuthatch (Sitta neumayer) and the eastern rock nuthatch (Sitta tephronata). Both species feed on insects in the soil. The size of the beak of each species determines the size of prey it can catch. Both nuthatches have a beak 26 mm in length, and therefore, it could be assumed that they will feed on insects of the same size, and that they will be in direct competition with one another. However, this is not the case in nature. In those areas where their distribution ranges overlap, the western rock hatch develops a beak 24 mm in length, while the beak of the eastern rock nuthatch grows to 29 mm! In areas where they do not overlap, and where they are not in competition, both species have a beak 26 mm in length [11]. This phenomenon is called character displacement. It is seen in the fact that species that come into competition in overlapping range areas will change those characteristics that create the competition between them. Is there competition among plants? Plants resolve possible competitors through allelopathy. This is a phenomenon in which some plants secrete chemical compounds into the soil to inhibit the growth of other plants. For example, walnut or sage secretes

2.2 Conditions for life

25

compounds into the soil that will disable the group of other plant species to with a radius of several metres from the plant. Predation Another important biotic factor that can influence the distribution of a given species is predation. This is the relationship in which one organism, the predator, consumes another, the prey. The prey is alive when the predator first attacks! Predators can overhunt and completely eliminate prey species from a certain area, or they can disable range expansion and colonisation of new areas by potential prey. Though there is theoretical support for such a possibility, there is no actual proof that this occurs in nature. Such extreme events are only known to occur in cases of introductions of species that are not native to an area. The influence of a predator on the prey population is evidently detrimental. However, predator effects on a prey population are not always easily predictable. There are two reasons for this: prey individuals that are killed or damaged do not always correspond to the random pattern of the entire prey population. Predators tend to select the prey that is easiest to catch: the young (and naïve), the old (and weak) and the sick (and helpless). Second, predation can impact the growth, survival and reproduction of prey. In other words, while predation is harmful to the prey individuals that are captured and consumed, it can be favourable to those individuals not captured. The case of the Kaibab deer is well known [12]. The initial population of 4,000 of these animals on the Kaibab Plateau, located in northern Arizona in the United States along the northern border of the Grand Canyon, grew to 100,000 in just 20 years (1905–1924), as humans hunted and eliminated their natural predators (the cougar and coyotes), Figure 2.5. This massive population growth resulted in great competition, primarily for food resources, and within the next 15 years, the population

Number of individuals (in thousands)

100

80

60

40 20

0

1910

1920

1930

1940

Year

Figure 2.5: Changes in abundance of Kaibab deer after elimination of natural predators [inspired by www.biologycorner.com/worksheets/kaibab_key.html, Keeton Biological science].

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declined to 10,000 individuals. Therefore, it could be concluded that the relationship between predator and prey is what maintains the natural balance! It is also important to note which prey individuals are under the effect of predators and during which life stage. Young individuals cannot yet contribute reproductively to the population, and therefore the effects of predation of this segment of the prey population are less than if the predator catches a reproductively mature individual. The impact of a predator on prey is not constant, and is instead limited to certain time periods. For example, the boa constrictor (Boa constrictor) will rest for a while after eating its prey, while it digests. The success rate of hunting prey is not always 100 %, as prey may escape. Also, some predators take the time to learn how to hunt, and their efficacy will change with age: the young tiger or lion are less experienced and effective than adult individuals. Parasitism Parasitism is a relationship that is similar to predation. It could be said that parasitism is a special form of predation, in which the predator is most often much smaller than its prey (host). Unlike “classical” predators, the parasite typically does not kill its prey. This is a relationship in which the parasite has a benefit, while the host typically experiences more or less damage. As in predation, parasites are one means of regulating the natural balance. They maintain their host populations to a certain level, to ensure that they will not be left without a food source. However, introduced parasites can cause significant changes in the distribution of potential host populations. Lake trout (Salvelinus namayscush) is a widely distributed species throughout northern North America, but it is not adapted to the presence of parasitic lampreys (Petromyzon and Entopshenus). These lampreys attach to fish and feed off their tissue and bodily fluids. Niagara Falls is a natural barrier preventing the entry of these parasites into the Great Lakes, where large populations of lake trout thrived. However, with the construction of the Welland Canal, connecting Lakes Ontario and Erie, the lampreys spread throughout all the Great Lakes and caused substantial declines in the lake trout populations [13]. A similar effect was seen following the introduction of the parasite that causes malaria in birds (Plasmodium) to the Hawaiian Islands. The endemic bird fauna of these islands suffered significant population declines of some species, range contractions and even extinctions [14]. Mutualism Mutualism is a relationship in which both species benefit. This relationship can imply a close physical interaction between members. Typically, one member of such a pair becomes completely dependent on the other, and for this species, this mutualism is obligatory. In extreme cases, in their interactions, these organisms begin to function as a single individual, as in the case of fungi and algae in lichens. One such example of obligate mutualism is the protozoans and bacteria in the digestive tracts of certain animals, such as ruminants or termites. Protozoans in the digestive tract of termites

2.2 Conditions for life

27

break down wood into compounds the host can digest further. Neither of these organisms would be able to survive on their own. Mycorrhiza is another form of mutualism. This is a symbiosis between the roots of a vascular plant (tree) and fungi. The fungi supply the tree with nutrients, while the plant supplies the fungi with carbon. However, mutualism may also be facultative (not obligatory), in which mutualists can survive normally without one another. The most common example of this form of mutualism is the hermit crabs and certain sessile anemones. The hermit crab settles in an empty snail shell, upon which one or more anemones can settle. The anemones defend the crab with their stinging cells, and since they are sessile organisms, the crab serves as their “means of transport.” However, both of these organisms can survive without the other. A special form of mutualism can also be seen in the relationship between certain plants and insects (or birds) as pollinators. Coevolution has gone very far here, as can be witnessed in the form of flowers, colouration and special mechanisms developed by plants and their pollinators. The most unusual examples of mutualism can be seen in the relationship between ants and certain plants. The South American species of acacia (Acacia) have thorns in which some ant species of the genus Pseudomyrmex built their nests [15]. The plant contains the protein-rich Beltian bodies (resembling berries) and the sweet fluids that the ants feed on. In return, they protect the plant from attack by other herbivorous insects and vertebrates. They also eliminate the surrounding vegetation, thus reducing competition with other plants. This specialisation has resulted in identical distribution ranges for these two species. Commensalism Commensalism is a relationship in which one species benefits, and the second neither benefits nor suffers. The Adriatic Sea is home to small soft-bodied crabs of the family Pinnotheridae, which are in commensal relations with numerous bivalves, ascidians and the pipes of the polychaete worms (Polychaeta). Among the many genera and species, the most common are the crabs that inhabit the noble pen shell and the crabs that inhabit oyster and mussel shells. The bivalves are not disturbed by these small crabs, which are seeking shelter from predators. Another example of commensalism is epiphytic plants. These are mostly tropical plants characteristic as living on the branches of other plants. They use only space on which organic material and water has collected, and have no other impact on the host plant. 2.2.3 Community No organism in nature lives in complete isolation. A collection of organisms interacting directly or indirectly in a habitat is a community. The concept of community is based on the efforts of botanists to group certain plant formations. In the early twentieth century, American scientist Frederic Clements [16] proposed that the plant units, which he called the “association,” are strictly determined and fixed for a long period of time. Today, the term “community” involves a group of all living

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organisms in the same habitat where among them there are relations of mutual dependence and biological connections. Their interaction is important for the functioning of the community. 2.2.3.1 Community structure The community is characterised not only by a mixture of species, but also by physical features. On land, the vertical structure of the community is mostly determined by plants. Their height, branching and the amount of leaves, determine temperature, moisture and light vertical gradient (Figure 2.6). Plants make the framework of the community in which animal species are adapted to. A well-developed forest ecosystem contains several layers of vegetation. There are the canopy layer, the understory, the shrub layer, ground layer and the forest floor. The most important role in the fixation of sun energy has a canopy. Aquatic systems, like lakes and oceans, are also vertically stratified primarily by penetration of light.

Emergent Layer

Upper Canopy

Understory/ Lower Canopy

Florest Floor

Figure 2.6: Forest vertical structure and light vertical gradient.

The horizontal pattern of community in space is variable. Usually, it includes differences due to latitude and altitude. Increasing latitude and altitude means more extreme conditions, and therefore the composition and appearance of the community changes. 2.2.3.2 Community sustainability In the early twentieth century, two American scientists, Frederic Clements and Henry Gleason, prompted the question of community sustainability (equilibria).

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29

Clements [16, 17] developed an “organism concept of community.” In the concept, each species in the community representing an interacting component of the whole. The main processes shaping the community are mutualism and coevolution (predator–prey or competition interactions). On the other hand, Gleason [18, 19] supported “the individualistic continuum concept.” The community very rarely (almost never) reaches a state of equilibrium. Communities, therefore, are not highly regulated species groups, but rather random populations of plants and animals, in which each individual responds to changes in the environment specifically. Biological factors, such as competition and predation, have no significant impact on community sustainability or equilibria. Many studies have been conducted in order to prove one of these theories in the last 50 years. Some have shown that predation and competition play an important role in regulating the community. Rapid change in the physical environment can strongly affect the composition and structure of the community. Climate change, weather or natural disasters can also affect communities significantly. 2.2.3.3 Biodiversity Biological diversity (biodiversity) is the variability of life on Earth. It includes genetic variation, ecosystem variation and species variation [20] within an area, biome or the whole planet. Diversity is estimated on the basis of species richness (number of species) and species abundance (the number of individuals per species). For estimation of biodiversity, many indexes are used, the most common is Shanon index: H= −

s X ðpi Þðlog2 pi Þ i=1

where H is a diversity of species, S is the number of species, and pi is the proportion of individuals in total sample belonging to the ith species. The number of species is changing over time (Figure 2.7). The oscillations of diversity and extinction rates are a consequence of changes in a number of factors: biotic and abiotic. It is believed that the biggest impact has a climate change [21]. Human activities disrupt the natural balance. This caused the extinction of many organisms, especially in the last century. 2.2.4 Ecosystem The concept of the community includes only living organisms in a habitat but ignores the physical environment: nutrients and energy that allow living organisms survival. The ecosystem is a spatial or organisational unit of organisms and their physical environment. The environment is consisting of biotic and abiotic components linked together through nutrient cycles and energy flow. Simply said, all ecosystems

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(terrestrial and aquatic) have three important parts: producers, consumers and the non-living environment (Figure 2.8). Long-Term Trend The“Big 5”Mass Extinctions

Thousands of Genera

5

Other Extinctions Events

4

3 2 1 0 N 0

Pg

K

50

100

150

P

Tr

J 200

250

C 300

D 350

S

400

O 450

Cm 500

542

Milions of Years Ago Figure 2.7: Apparent marine fossil diversity during the Phanerozoic; N – Neogene, P – Paleogene, K – Cretaceous, J – Jurassic, Tr – Triassic, P – Permian, C – Carboniferus, D – Devonian S – Silurian, O – Ordovician, Cm – Cambrian, inspired by [22].

ECOSYSTEM BOUNDARY ORGANIC COMPARTMENT

Ab ga sor dr ses tion y d , w of ep et Re os an ev leas iti d ap es on or o ati f g on as es ,

Weathering

SOIL AND ROCK MINERAL COMPARTMENT

Formation of secondary minerals

Litter

Herbivore carnivore omnivore detritivore

Living plant biomass

Dead biomass

AVAILABLE NUTRIENT COMPARTMENT On exchange sites

Meterological geological biological

INPUT

Mineralization Ieaching, throughfall, stemflow, exudation

Dry deposition impaction

Inorganic aerosols

windblown particulates and gases above-and belowground

Biological uptake of gases Biological release of gases organic aerosols evapotranspiration

Biological uptake

ATMOSPHERIC COMPARTMENT

BIOSPHERE

OUTPUT Meterological geological biological

In soil solution

INTRASYSTEM CYCLE

Figure 2.8: Schematic representation of the ecosystem; inspired by [23].

The energy that flows through ecosystems is obtained primarily from the sun. It generally enters the system through the process of photosynthesis. The energy

2.2 Conditions for life

31

accumulated in the process is called primary production. Total annual primary production on Earth is 162.41 × 109 t. Approximately 1/3 of it occurs in the sea, and the rest on the land. Among the most productive ecosystems in the world are wetlands; however, their share in global production is small because they cover a very small part of the earth’s surface. In terrestrial systems, production is determined by temperature and precipitation, because those directly affect the level of photosynthesis. In the oceans, production is limited by the penetration of light. The phytoplankton (and plants) are located mainly in the surface layers of aquatic ecosystems, where there is enough light. However, the primary production also depends on the amount of nutrients: nutrients from deeper parts must be transported in the surface layers. The energy stored in plants is going through ecosystem in series of steps called food chains. A food chain shows how the organisms are related to each other by the food they eat. Each level of a food chain represents a different trophic level, but all of them starting from producer organisms (plants) and ending at apex predator species (carnivore). One kind of plant can be a source of food for many herbivores, but also many carnivores can hunt the same prey. So actually, in the ecosystem, many food chains interconnected in food webs. Organisms in the food chain can be grouped according to the type of food they consume, in trophic levels. In general, all organisms that feed on other organisms are called consumers or secondary producer. Consumers can be divided into subgroups, each of which represents a single trophic level: those which feed on plants (primary producers) are called herbivores or primary consumers. Carnivorous (meat-eating) or predators feed on herbivores (plant eaters) and are called secondary consumers. Almost every habitat, including freshwater ecosystems, includes consumers who do not fit entirely into this simple scheme of trophic levels. These are consumers – decomposers or detritivores, they feed on dead remains of other organisms (detritus). Their role may at first glance do not seem so important, but they are an important link in the flow of energy and nutrient circulation in the ecosystem. Decomposers are involved in the degradation of dead plants and animals, returning nutrients in the cycle and thus allowing growth and development of primary producers. The amount of energy that is transferred from one trophic level to another is very difficult to determine. When summed, biomass, or energy on each trophic level, constructs an ecological pyramid. It is also called Elton’s pyramid, according to Elton [24]. In general, biomass and energy of producers must be greater than the biomass and energy of secondary producer: base of the pyramid determines the size of each of the next trophic level (Figure 2.9). According to the second law of thermodynamics, as energy transfers between different trophic levels, there is a loss in the form of heat which limits the number of links in the chain. Highly productive systems do not support long food chains; however, they have a lot of species. This means that their food web is very complex. It is also known that ecosystems which are subject to rapid changes in abiotic factors

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Energy pyramid

teritiary consumers

secondary consumers

energy “lost” (heat) primary consumers

producers

energy transferred

Figure 2.9: Energy pyramid.

have shorter food chains in relation to those stable. Highly stratified systems such as forests or pelagic ocean food chains are longer than those less stratified (meadows, tundra, benthal of a stream). 2.2.4.1 Biogeochemical cycles All nutrients are transported through the ecosystem from the non-living to the living components in cyclic paths called biogeochemical cycles. The most important biogenic elements such as carbon, nitrogen, phosphorus and sulfur are bound in living organisms in the food chains and, through the process of decomposition of dead organisms, again returned to the lithosphere. Then the whole cycle begins again (Figure 2.10(a)). The main driver of all is the solar energy and is unusually important role for all biogenic elements has a water cycle (Figure 2.10(b)). Carbon, hydrogen, oxygen, nitrogen, phosphorus and sulfur make 95 % of the biomass on Earth and are called macroelements. Macroelements together with calcium, silicon, magnesium, sodium, potassium, chlorine and iron (micro elements) consist 99 % of the dry weight of living organisms. Other biogenic elements (manganese, molybdenum, copper, vanadium, nickel) appear in much lower concentrations and a group of trace elements. 2.2.4.2 Ecosystem biodiversity and stability One of the basic questions in ecology is: how many species is necessary for the normal functioning of the ecosystem? Is there a minimum or, if they are redundant species in the system? If there are redundant species: which species are necessary for the maintenance of the ecosystem?

2.2 Conditions for life

33

Abiotic poor or sink e.g., atmosphere ocean

Other obiotic pool sink e.g., soil Biotic component

condensation

evaporation

precipitation

transpiration

percolation

Figure 2.10: (a) nutrients cycle; (b) water cycle; (c) nitrogen cycle.

If we assume that all species are essential for the functioning of the ecosystem, then the loss of any causes imbalance: leads to degradation or collapse of the whole system (Figure 2.11). Maybe a diversity of species in ecosystem has no influence on its function, so the loss of any species causes random and unpredictable consequences.

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Rate of ecosystem function

Rate of ecosystem function

34

(a)

Number of species

(b)

Number of species

Figure 2.11: The potential relationship between the number of species in the ecosystem and its functioning (primary production, decomposition, circulation of materials); (a) redundant species hypothesis; (b) hypothesis dependent species [25].

These models were tested in the laboratory and in situ. The first laboratory research on this subject was conducted by John Lawton with a group of researchers at the Imperial College in London [26]. They found that ecosystems with a large number of species have more efficient primary production and developed a complex plant cover, but also accumulate more nutrients. Their results support the second hypothesis: that the reduction of biodiversity causes poorer functioning ecosystem. However, it is possible that further addition of species in a system causes a certain saturation point so that this experiment does not answer the question posed at the beginning. In any case, this research demonstrates that we can reject the third hypothesis: the functioning of the ecosystem is not random in relation to biodiversity. The group of authors from the University of Minnesota conducted similar studies [27]. Their results were similar to Lawton’s research: greater biodiversity – a better functioning of the ecosystem. However, they found that all species in the system are not equally valuable. The value indicates how much the loss of a certain species impacts the entire ecosystem, but also that some species depend on each other. For example, plants belonging to family (Fabaceae) legumes are very important for the nutrient cycling in the ecosystem, since their roots have symbiotic bacteria that can bind elementary nitrogen. Circulation of nitrogen is one of the basic biogenic cycles that is important for all organisms. By fixing nitrogen, these plants provide more nutrients in the soil, which in turn results in greater production of other plants, and animals, which are connected to them in the food chain. Therefore, the loss of legume species can have a major impact on the production of the entire system. These species are often called and “keystone species,” in terms of their importance to the functioning of a system. Another issue is of extraordinary importance when it comes to biodiversity and ecosystem function: whether biodiversity influences the stability of the ecosystem? British ecologist Charles Elton during the 1950s observed that more complex and richer types of systems are less susceptible to the influence of sudden changes.

2.2 Conditions for life

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However, the development of mathematical modelling and the use of simulation in the population ecology did not to reach the same results. Models showed that the populations of some species even in diverse ecosystems are subject to fluctuations caused by external factors (disease, drought, etc.). It is possible that regardless of variations in individual species, the functioning of the entire ecosystem remains unchanged. So, the population of a certain species may fall or rise, but ecosystem survives because there are a lot of other populations that still maintain the function of the system. 2.2.5 Succession Communities in an ecosystem are changing over time. Such changes are called succession. Actually, it would be more accurate to say that the succession is a series of changes in communities within a certain time period. Succession occurs in both terrestrial and aquatic systems. We distinguish between so-called primary and secondary successions. Primary succession takes place on previously completely bare surfaces (without life). Secondary succession happens to already populated habitats after a disturbance. On August 28, 1883, at 10:02 pm there was an extraordinary disaster. The Indonesian island of Krakatoa exploded in one of the largest volcanic eruptions in recent history. Most of the island was blown off in the explosion. At the site of the former island of Krakatau was born two smaller islets: Anak Krakatau and Rakata. The island of Rakata was completely sterilised: the entire island was covered with a layer of lava 30–60 m thick, and all life on it was destroyed. The first expedition came to Rakata 8 months after the explosion and found only one living creature on the island: one spider! Scientists continue to explore settlement of animals and plants on this completely bare area. After 3 years, the first living organisms were observed on the island: the blue-green algae inhabited areas of cooled volcanic ash. Along came mosses, they are the pioneer species that first colonists of a habitat. Pioneer species created the basis for the settlement of other organisms. After 25 years, the tropical forest appeared and with it the characteristic fauna of birds, snails, butterflies, bats, etc. In 1983, scientists counted a total of 420 taxa on Inland Rakata (Figure 2.12). During the colonisation of the island Rakata, several communities replaced one after another. In succession, plants are always preceded the animals, creating a habitat for them.

2.2.5.1 Climax According to the classical ecological theory, succession ceases when species of late successional stages become dominant. At this point, the community has achieved stability, and any disturbance cannot significantly change the system. This final point of succession is called the climax.

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500

Nuber of species

400

300

200

100

0 1883

1903

1923

1943

1963

1983

Year Figure 2.12: The number of species on Rakata in time, after Krakatau explosion; inspired by [28].

Community climax theoretically has certain characteristics: community achieved the balance between total primary production and total respiration; energy obtained from sunlight and decomposition; between the consumption of nutrients and nutrients returned by a process of decomposition. Each individual in the stage of climax is replaced after the death with another individual of the same species; species composition is actually in a state of equilibrium. Many communities that seemingly appear balanced actually undergo successive changes a lot more often than we perceive. Tropical forests in Central America are exposed to frequent natural disasters. Tropical storms and hurricanes occur very often in this area and have a great impact on the communities. According to some calculations, tropical storms affect the same area (community) every 60 years, leaving behind devastation: broken trees or full or partial defoliation of vegetation. Destruction of vegetation cover, of course, affects the wildlife causing also a different composition and distribution of animal habitats. Therefore, climax should be considered as a dynamic equilibrium of the community. Even “old” and apparently stable community is constantly in the process of dynamic change.

2.2 Conditions for life

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2.2.6 Biomes

Co ld

Climate largely determines plant formations and life in them. These formations are called biomes. There are several major terrestrial biomes: tundra, grassland, desert, taiga, forest temperate zone, Mediterranean vegetation and tropical rainforest. They are further divided into types depending on the climate and altitude (Figure 2.13).

Artic

ra tur e

Tundra

De ac res ing

tem

pe

Subartic

Taiga

Temperate Temperate grassland

Desert

Ho t

Temperate forest

Tropical

Rain forest

Savanna

wet

Desert Dry

Deacresing temperature

Figure 2.13: Biomes; inspired by [29].

Although inland water (freshwaters) account just a little bit over 0.5 % of all water on Earth, its importance is very high. It is used as drinking water, in industry and agriculture. Inland waters are groundwaters and surface waters. Surface waters are running waters like rivers and streams and standing waters like pools, ponds and lakes. Seas and oceans cover more than 70 % of the Earth’s surface and are inhabited by living organisms from the surface to bottom. The chemical composition of sea water is very stable, more than 85 % of the total amount consists NaCl. Temperature fluctuations of the surface layer depend on the geographical location. In addition to temperature, pressure has a significant impact on life in the sea. Pressure increases with depth. Deep layers have a constant temperature, while in the surface layers (up to 200 m) temperature varies. There are two main habitats in the sea: bottom and water column. The sea bottom is very diverse habitat it is inhabited by benthic organisms. Plankton and nekton organisms live in the water column. 2.2.7 Global changes Today, human activities cause environmental changes that disturb the normal functioning of the biosphere. Major changes are greenhouse effect that causes the global warming, ozone depletion, acid rains and the destruction of habitats.

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2.2.7.1 Greenhouse effect In the last 100 years, the concentration of CO2 in the atmosphere has increased about 25 % particularly due to a greater exploitation and use of fossil fuels. Excessive amounts of CO2 in the Earth’s atmosphere are causing the greenhouse effect. The earth’s surface absorbs solar radiation and then transmits it as longwave radiation or thermal energy. CO2 traps longwave, thus heating up the Earth’s atmosphere. This effect is called the greenhouse effect and causes global warming. According to some predictions, by the year 2100, the average temperature on Earth will increase in about 2 °C. The consequences could be climate change that can lead to drastic changes in the distribution of individual plant and animal species, which in turn can lead to problems in food production, and transmission of various diseases (malaria, influenza and yellow fever). 2.2.7.2 Acid rains Precipitation such as rain and snow have naturally slightly acidic pH: between 5 and 5.6 (due to a certain amount of CO2 in the air). Acid rain is any precipitation with pH lower than 5. Such acidic precipitation is caused by higher amounts of various air pollutants particularly sulfur dioxide (SO2) and nitrogen oxides (NOx). Precipitation with low pH damages plants, causes acidification of lakes and rivers and directly influences the living world in them. Acid rain may also cause acidification of soil. The consequences of this are heavy metal leeching in terrestrial and aquatic ecosystems. Heavy metals are toxic to living organisms: in vertebrates, they are deposited in the liver and brain and can cause serious damage to these organs. 2.2.7.3 Ozone depletion Ozone, O3, is a form of elemental oxygen that is important for the absorption of ultraviolet radiation in the stratosphere. It absorbs 99 % of UV radiation which can cause severe damage to DNA. The depletion of the ozone layer can be caused by freons (a number of halocarbon products which have typically been used as refrigerants and as aerosol propellants), the detonation of nuclear weapons and the exhaust gases over large urban centres. 2.2.7.4 Habitat fragmentation We already at the beginning of this chapter emphasised that the human’s impact on nature is great. One of the global environmental problems is the destruction of habitats. Construction of roads, railways, power lines, expansion of settlements and agricultural land use caused the destruction of natural habitats and/or their fragmentation. Such fragments of natural habitat are often insufficient to maintain populations. One of the major problems of habitat destruction is certainly deforestation, particularly in the tropics. In addition to degradation of the forest community, it also causes a drastic climate change.

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2.2.8 Applied ecology 2.2.8.1 Constructed wetlands Constructed wetlands are treatment systems designed for the purpose of improvement of water quality. They use natural processes involving wetland vegetation, soils and associated microbial assemblages in treating anthropogenic discharge such as municipal or industrial wastewater or storm water runoff. Constructed wetlands can be designed to emulate the features of natural wetlands, such as acting as biofilters for removing sediments and pollutants from the water. Some constructed wetlands may also serve as a habitat for native and migratory wildlife, although that is usually not their main purpose. Vegetation in a constructed wetland provides a substrate (roots, stems and leaves) upon which microorganisms can grow as they break down organic materials (Figure 2.14 and Figure 2.15). The plants remove about 7–10% of pollutants and act as a carbon source for the microbes which are responsible for approximately 90 % of pollutant removal.

Emergent plant

Water level

Flow in

Plant litter to mulch/detritus layer

Precip

Leaching of BOD, N, P from mulch/detritus layer

N, P uptake by plants Flow out

Impermeable liner Attached growth of bacteria gravel media

Figure 2.14: Constructed wetland; inspired by [30].

2.2.8.2 Water framework directive Freshwater ecosystems are among the most degraded on the planet. Numerous human activities impact water quality, including agriculture, industry, urbanisation, disposal of human waste, mining and climate change. In 2000, the European Union established its framework for the protection, improvement and sustainable use of Europe’s water resources by launching the Water Framework Directive (WFD) [31]. The WFD is considered to be pioneering because it champions the

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Figure 2.15: Constructed wetland in location Hrušćica near Zagreb; photo by Renata Horvat.

ecosystem approach, that is, the integrated consideration of chemical and ecological status in defining water quality [32]. Although the Directive requires the assessment of hydromorphological and physico-chemical elements, a biological assessment is given priority. The assessment of the ecological status establishes the analysis of the structure of biological communities of macroinvertebrates, fish, macrophytes, phytobenthos and phytoplankton. Figure 2.16 illustrates how these various elements are combined and how the “one-out, all-out” principle is applied. Measuring ecological status makes it possible to evaluate the effect of human activity on water ecosystems, and it will be an essential tool for the sustainable management of water resources. The legislation requires the periodic assessment of all water bodies, including rivers, lakes, estuaries, coastal waters and groundwaters. The first and basic step in the implementation of the WFD in the segment of surface waters is their typification, so that a type-specific approach to estimation water quality could be applied [33]. Water types are then assigned to a classification system that grades their deviation from reference state (high, good, moderate, poor and bad), with no, or very minor, disturbance from human activities. In Croatia, 19 river types were identified and large river types were intercalibrated at EU level. The WFD requires the EU Member States to develop classification systems to describe the ecological status of a given water body at a given time. The main objective of the WFD is to implement measures to achieve “good ecological status” of all natural water bodies. The emphasis given by the WFD to ecological elements has been widely welcomed by scientists and environmental managers as it focuses risk management efforts on restoring those impacted ecosystems that are classified as being of less than “good ecological status.”

References

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Ecological Status

Surface Water Status

Figure 2.16: Classification scheme of surface water status using “one-out, all-out” principle; H – high status, G – good status, M – moderate status, P – poor status, B – bad status.

References [1] [2]

[3] [4] [5] [6] [7] [8]

Darwin C. On the origin of species by means of natural selection or the preservation of favoured races in the struggle for life. London: John Murray, 1859. Haeckel EH. Generelle Morphologie der Organismen. Allgemeine Grundzüge der organischen Formen-Wissenschaft, mechanische Begründet durch die von Charles Darwin reformirte Descendenz-Theorie. Volume I: Allgemeine Anatomie der Organismen. 32 + 574 pages; volume II: Alllgemeine Entwickelungsgeschichte der Organismen. 140 + 462 pages. Berlin, Germany: Georg Reimer, 1866. Shelford VE. Animal communities in temperate America. Chicago: University of Chicago Press, 1913. Krohne DT. General ecology, 2nd ed. Pacific Grove, CA: Brooks/Cole, 2001. Postlethwait JH, Hopson J. The nature of life. New York: McGraw-Hill, 1992. MacArthur RC, Wilson EO. The theory of Island biogeography. Princeton: Princeton University Press, 1967. Connell JH. The influence of intra-specific competition and other factors on the distribution of the barnacle Chthamalus stellatus. Ecology 1961;42:710–723. Jelić D, Duplić A, Ćaleta M, Žutinić P. Endemske vrste riba jadranskog sliva. Zagreb: Agencij a za zaštitu okoliša, 2008.

42

[9] [10] [11] [12] [13] [14] [15] [16] [17] [18] [19] [20] [21] [22] [23] [24] [25] [26]

[27] [28] [29] [30]

[31]

[32]

[33]

2 Ecology

UNEP-WCMC. Review of the grey squirrel Sciurus carolinensis. Cambridge: NEP- WCMC, 2010. Bukvić I. Trofička struktura makrozooplanktona u krškim jezerima Visovac i Vrana (Cres). Disertation, Zagreb: Faculty of Science, University of Zagreb, 1998. Grant PR. Convergent and divergent character displacement. Biol J Linnean Soc 1972;4:39–68. Rasmussen DI. Biotic communities of Kaibab Plateau, Arizona. Ecol Monogr 1941;11:229–275. U.S. Geological Survey, Nonindigenous aquatic species, Petromyzon marinus Available at: https://nas.er.usgs.gov/queries/FactSheet.aspx?speciesID=836). Accessed: 6 Feb 2017. Warner RE. The role of introduced diseases in the extinction of the endemic Hawaiian avifauna. Condor 1969;70:101–120. Janzen DH. Coevolution of mutualism between ants and acacias in Central America. Evolution 1966;20:249–275. Clements FE Plant succession: Analysis of the development of vegetation. 1916, Carnegie Institute of Washington Publications 242, 1–512. Clements FE. Nature and structure of the climax. J Ecol 1936;24:252–284. Gleason HA. The individualistic concept of the plant association. Torrey Bot Club Bull 1926;53:7–26. Gleason HA. The individualistic concept of the plant association. American Midland Naturalist 1939;21:92–110. Gaston KJ. Global patterns in biodiversity. Nature 2000;405(6783):220–227. Cox B, Moore PD. Biogeography: an ecological and evolutionary approach, 7th ed. Oxford: Wiley-Blackwell, 2009. Rosing M, Bird D, Sleep N, Bjerrum C. No climate paradox under the faint early Sun. Nature 2010;464(7289):744–747. Krohne DT. General ecology. Pacific Grove: Brooks/Cole,Thomson Learning Inc., 2001. Elton C. Animal ecology. London: Didgwick & Jackson, 1927. Lawton JH. What do species do in ecosystem? Oikos 1994;71:367–374. Naeem S, Thompson LJ, Lawler SP, Lawton JH, Woodfin RM. Empirical evidence that declining species diversity may alter the performance of terrestrial ecosystems. Phil Trans R Soc London B 1995;347:249–262. Symstad AJ, Tilman D, Wilson J, Knops MH. Species loss and ecosystem functioning: Effect of species identity and community composition. Oikos 1998;81:389–397. Whitaker RH. Plant recolonization and vegetation succession on the Krakatau Island. Ecol Monogr 1989;59:59–123. Whitaker RH. 1989 communities and ecosystem, 2nd ed. New York: Macmillan, 1975. Tilley E, Ulrich L, Lüthi C, Reymond P, Zurbrügg C. Compendium of sanitation systems and technologies, (2nd Revised Edition). Duebendorf, Switzerland: Swiss Federal Institute of Aquatic Science and Technology (Eawag), 2014. EU. Directive 2000/60/EC of the European Parliament and of the Council establishing a framework for the Community action in the field of water policy – EU Water Framework Directive (WFD), 2000. Vincent C, Heinrich H, Edwards A, Nygaard K, Haythornthwaite K. Guidance on typology, reference conditions and classification systems for transitional and coastal waters. CIS Working Group 2.4 (COAST), Common Implementation Strategy of the Water Framework Directive, European Commission, 2002. Mihaljevic Z. Typology of non-stagnant waters in Croatia based on macrozoobenthos community (In Croatian with English summary). Hrvatske Vode 2011;76:93–180.

Study questions

43

Study questions 1. 2.

3.

What do several different populations living together make? A) a biosphere; B) an organism; C) a community; D) an ecosystem When there is a lot of pollution, rain can be acidic, harming plants and animals. What is this an example of? A) competition between a population and a community; B) a mutualistic type of symbiosis; C) an abiotic factor affecting an ecosystem; D) an individual affecting a community Bears eat fruits such as berries and animals such as fish. They hibernate in the winter. Which of these terms applies to bears? A) they have a mutualistic relationship with berries; B) they are at the bottom of the energy pyramid; C) they are decomposers; D) they are consumers.

Population time

D

C

B

A 0 time

4. The carrying capacity of the environment, for the population shown in the diagram, is the best represented by a point on the curve marked with a letter: A) A; B) B; C) C; D) D. Table 1: Population density. Level

Population

1 2 3 4

53 361 823 6283

5.

In a simple ecosystem, a census of the populations in four successive trophic levels was taken as shown in the Table 1. If Level 1 is composed of photosynthetic autotrophs, then the trophic level with 823 individuals will most likely represent? A) primary consumers; B) secondary consumers; C) decomposers; D) producers.

44

2 Ecology

6. What effect does biodiversity have on a community? A) it makes destruction by insects impossible; B) it makes primary succession more likely; C) it enables species to survive in a desert; D) it enables the community to withstand changes. 7. Precipitation and evaporation are important components of the A) nitrogen cycle; B) water cycle; C) carbon cycle; D) phosphorus cycle. 8. Match each item with the correct statement: A) the populations in an ecosystem 1) food web B) made up of interconnected food chains 2) abiotic C) the model that shows feeding relationships 3) food chain D) living things in an ecosystem 4) biotic E) non-living things in an ecosystem 5) community 9. A certain area in north-west Europe (peatlands) store 30 million tonnes of carbon. In pristine condition, these peatlands can store an additional 15,000 tonnes of carbon per year. A) Given this rate of productivity, how long would it take for the peatlands to sequester this much carbon? B) One prediction of climate change models is a reduction in rainfall in this part of Europe. This would transform the peatlands into a carbon source, emitting up to 462,000 tonnes of carbon per year. How many years would it take to respire all the carbon stored in the peatland? C) What is the effective residence time of the carbon that makes it into long-term storage in the peatland if there is no disturbance in the ecosystem? (Note: it is not a calculating problem!) 10. Base your answer to the following question on the diagram below. A pair of wild goat, A, lives on 1 square kilometre of land. A second pair, B, lives on 4 square kilometres of land, in which 0.25 of the 4 square kilometres overlaps the territory of the first pair.

B A

Both pairs A and B are members of the same species. Which of the following explains why area B is larger than area A? A) Pair B is bigger; B) Pair B has less food in its area; C) Pair A has fewer offspring D) Pair B has more available resources.

Study questions

45

Solutions 1. C; 2. C; 3. D; 4. B; 5. B; 6. D; 7. B; 10. B; 8. A) the populations in an ecosystem 5) community B) made up of interconnected food chains 1) food web C) model that shows feeding relationships 3) food chain D) living things in an ecosystem 4) biotic E) non-living things in an ecosystem 2) abiotic 9. A) 30,000,000 tonnes C / 15,000 tonnes C yr-1 = 2000 years; B) 30,000,000 tonnes C / 462,000 tonnes C yr-1 = 64,9 years; C) Theoretically, infinite: the net community productivity is stored in peat indefinitely.

Tomislav Bolanča, Šime Ukić and Mirjana Novak Stankov

3 Environmental Chemistry Abstract: Environmental engineers need to be good in chemistry because pollutants are chemicals too and, in order to fight the pollution, they should know the properties of these chemicals. Environmental chemistry is a scientific discipline that studies chemical principles, analyses the environment and uses the obtained results in understanding of the processes occurring in environment. The discipline has arisen due to the recognition that chemical compounds, whether anthropogenic or natural, have important effects on naturally occurring processes and organisms. One of the goals of the discipline is to quantify these effects through controlled experiments and measurements. Using the above mentioned approach, a fundamental understanding of the chemical processes occurring in a given system can be achieved. This chapter is dealing with fundaments of Environmental chemistry. Keywords: environment, chemistry, chemical engineering

3.1 Introduction Most of environmental problems and processes have chemical nature. Therefore, being familiar with basics of environmental chemistry is crucial for understanding of processes that directly affect the environment. The basics of environmental chemistry are strictly related with chemical equilibrium phenomena that are explained in this chapter. This article is focused on physical-chemical phenomena that occur in water, soil, and atmosphere. Phenomena related to biosphere will be discussed elsewhere. Chemistry of water, soil, and atmosphere environment can be discussed separately. However, one should be aware that each of these three environments: water, soil or atmosphere, actually incorporates all three phases. This emphasizes importance of understanding chemical equilibrium as a foundation for any further upgrade that could help in explaining more complex environmental engineering problems.

3.2 Electrolytes and non-electrolytes Some substances dissociate to ions when dissolving in polar solvents. They are called electrolytes since, due to the occurrence of ionic species, this solutions conduct electricity. Further, those substances that do not show this ability are called nonelectrolytes. Electrolytes that dissociate completely (100 %) are called strong electrolytes, while those that show partial dissociation are weak ones. The degree of https://doi.org/10.1515/9783110468038-003

48

3 Environmental Chemistry

dissociation, i. e. degree of ionization, is commonly marked with Greek letter α and is defined as: α=

nDISSOCIATED MOLECULES nTOTAL AMOUNT OF MOLECULES

(3:1)

Letter n represents the amount of molecules of monitored substance expressed in moles.

3.3 Concentration and activity Concentration of electrolyte has significant influence on majority of equilibria that occur in solutions. Many experiments have shown that even presence of foreign electrolytes, i. e. the electrolytes that actually have no part in considered chemical reactions, can affect the related equilibrium. Moreover, electrolytes concentration is not the only factor that affects the equilibrium but the charge of the ions also. Scientists related these phenomena with a quantity called ionic strength of solution, I, which can be calculated according to eq. (3.2). I=

1 X ci
zi2
2 i

(3:2)

Symbol ci represents molar concentration of electrolyte’s ion i, while zi is the charge of the same ion. For low values of ionic strength (I < 0.1 M), electrolyte effect depends only on the strength value and has no relation with the kind of present ions [1]. There is lot of strong interactions in electrolytic environment and, accordingly, behavior of any ion in such environment is subjected by influence of the surrounding ions. Due to the interactions, many ions behave less active then they should be, so it seems like they are less concentrated than they really are. Such active or “effective concentration” is called the activity, a. Activities are related with actual molar concentration, c, through activity coefficient, γ: a=γ
c

(3:3)

For ideal solutions (i. e. highly diluted solutions) activity coefficient has value 1 and the activity is considered equal to the molar concentration. Activity coefficient decreases as the solution becomes more concentrated. Accordingly, it is lower than 1 in moderate concentrated solution so in these solutions activity differs from the molar concentration. Activity coefficient is related with the ionic strength of the solution and can be calculated according to Debye–Hückel equation: pffiffi A
zi2 I pffiffi − log γi = 1 + B
αi I

(3:4)

3.4 Ionization of water

49

Symbol γi is activity coefficient of ion i (single-ion activity coefficient), A and B are model constants (A = 0.512 and B = 3.3 for aqueous solution at 25 °C) [1], and α is effective diameter of hydrated ion i, expressed in nanometers. Debye–Hückel equation is usually used in simplified form for aqueous solutions at 25 °C with values of the ionic strength less than 0.01: pffiffi − log γi = 0.512
zi2 I

(3:5)

Mean activity coefficient, γ±, is also applied in many cases. This mean-value can be calculated as geometric mean of single-ion activity-coefficients of cation (+) and anion (–): pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi γ± = γ+
γ−

(3:6)

New form of Debye–Hückel eq. (3.5) can be obtained by incorporation of mean activity coefficient: pffiffi − log γ ± = 0.512
jz +
z − j I

(3:7)

Charge numbers, z, of cation and anion are marked with + and –, respectively. Obviously, it is more appropriate to use activity instead of molar concentration when describing some chemical system. Yet, in order to simplify the calculations and due to the fact that most chemical reactions occur in relatively diluted solutions, the chemists knowingly use concentration instead of activity. The authors applied same practice in this article. The exceptions are cases where difference between activity and real concentration has significant role in understanding of system behavior.

3.4 Ionization of water Johannes Nicolaus Brønsted and Thomas Martin Lowry gave probably the most common definition of acids and bases in 1923 [2, 3]. They defined acids as substances that can donate proton (proton donors) and, accordingly, all substances with the ability to accept proton (proton acceptors) were classified as bases. The substances that can behave either as acids or as bases are called amphoteric substances, i. e. ampholytes. Water is one of the amphoteric substances. Also, it is one of the most commonly used polar solvents. Due to its amphoteric properties, it shows effect of autoionization (eq. (3.8)). H2 OðlÞ ⇄ Hð+aqÞ + OHð−aqÞ

(3:8)

50

3 Environmental Chemistry

The obtained hydrogen ion is bare nucleus of hydrogen atom, i. e. it is a proton. Due to its positive charge, proton is attracted to any part of a nearby molecule in which an excess of negative charge exists. In the case of water solution, proton is attracted by the unshared pair of oxygen electrons from water molecule. So it is more correct to write H3O+ instead H+. Yet, for simplicity, the using of H+ symbol will remain, knowing that it actually represents hydrated proton, i. e. hydronium ion, H3O+ [4]. The equilibrium constant for chemical reaction (8) can be written as: K=

½H + 
½OH −  ½H2 O

(3:9)

The square parentheses in eq. (3.8) represent equilibrium concentrations. The concentration of water molecules in water solutions is practically constant and as such it can be incorporated into equilibrium constant. Let’s call this new constant the ionization constant of water and mark it as KW: KW = ½H + 
½OH − 

(3:10)

Ionization constant of water depends on temperature, just like all other constants of chemical equilibrium. At room temperature (25 °C) it has value of 1.01
10 − 14 M2 [5]. This determines water as very weak electrolyte. Concentration of ions in solutions might vary over large range of concentrations, meaning many orders of magnitude. Therefore, it is practical to use logarithmic scale while expressing the concentrations. Danish chemist Søren Peder Lauritz Sørensen introduced concept of “p-values” for this purpose [6]. The concept defines p-value as negative logarithm of an observed quantity. For example: pH = − log½H + 

(3:11)

pOH = − log½OH − 

(3:12)

pKW = − log KW

(3:13)

The value inside logarithm cannot have dimension. Therefore, it is important to emphasize that values of concentration used in the calculation must match mol/dm3 (shortly written as M) and values of equilibrium constant must be derived from equally expressed concentrations. For example, ionization constant of water must be expressed as 10–14 since this value relates M2 unit. This gives logKW value of 14. Accordingly, eq. (3.10) can be transformed into: pH + pOH = pKW = 14

(3:14)

51

3.5 Strong and weak acids

3.5 Strong and weak acids Let’s observe a hypothetic weak acid HA, consisted of proton and a hypothetic anion A–. In water solution, this acid reacts with the solvent and releases proton. HAðaqÞ + H2 OðlÞ ⇄ H3 Oð+aqÞ + Að−aqÞ

(3:15)

The constant that defines this equilibrium is called acid ionization constant, KA: KA =

½ H3 O + 
½ A −  ½HA

(3:16)

According to Brønsted–Lowry definition, HA is acid, while at the same time the obtained product A– is base since it can accept proton: Að−aqÞ + H2 OðlÞ ⇄ HAðaqÞ + OHð−aqÞ

(3:17)

Base A– is considered conjugate base of acid HA. Equilibrium for chemical reaction represented by eq. (3.17) is defined by base ionization constant, KB: KB =

½HA
½OH −  ½A − 

(3:18)

Equilibrium concentration of conjugate base A– can be expressed from eq. (3.18) and transferred into eq. (3.16) bringing a new equation: ½HA
½OH −  KB ½HA

KA = ½H3 O + 


(3:19)

Equation (3.19) can be additionally simplified to: KA
KB = ½H3 O + 
½OH − 

(3:20)

The obtained equation is the general relation that connects acids with their conjugate bases: KA
KB = KW

(3:21)

pKA + pKB = pKW = 14

(3:22)

Acids that act like strong electrolytes are called strong acids. The equilibrium constant for ionization of such acids, KA, tends to infinity, since the equilibrium concentration of non-ionized form of acid practically equals 0 M. The example of strong acid is hydrochloric acid, HCl.

52

3 Environmental Chemistry

Concentration of protons that originate from autoionization of water can be ignored during calculation of solution’s pH-value for cases where initial concentration of strong acid is significantly higher than 10–7 M. Since strong acids ionized completely, all protons at equilibrium state practically originate from the acid and the influence of water-originated protons is negligible. Problem 3.1. Calculate pH-value of 0.1 M HCl solution. HClðaqÞ

!

Hð+aqÞ 10 − 7 M

cACID

1Þ INITIAL STATE 2Þ EQUILIBRIUM

+

0

10

−7

M + cACID  cACID

Clð−aqÞ 0M cACID

½H +  = cACID pH = − log½H +  = − log c0 = − log 0.1 = 1

According to above performed calculation, general expression for pH-value of strong acids is: pH = − log cACID

(3:23)

Protons that originate from autoionization of water must be taken in consideration in cases when concentration of strong acid is not significantly higher or is even lower than 10–7 M. Problem 3.2. Calculate pH-value of 10–8 M HCl solution.

1Þ INITIAL STATE

HClðaqÞ cACID

2Þ EQUILIBRIUM

0

!

Hð+aqÞ cH +

form water autoionization

 cACID + cH +

form water autoionization

+

Clð−aqÞ 0M cACID

HCl is a strong electrolyte and it ionizes completely. This generates an amount of H+ ion equal to the concentration of HCl, i. e. 10–8 M. At the same time, 10 times higher concentration of protons is already present in water due to water autoionization. Therefore, concentration of protons from the autoionization must be taken in calculations. ½H +   cACID + cH +

form water ionization   −7

pH = − log½H  = − log 1.1
10 +

= 10 − 8 M + 10 − 7 M = 1.1
10 − 7 M = 6.96

Weak acids are weak electrolytes since they ionize partially. Calculation of pH-value for weak acids is somewhat different then for strong ones. Let’s observe weak acetic

53

3.5 Strong and weak acids

acid, CH3COOH, in water. At equilibrium state, the concentration of ionized molecules of acid, x, is negligible related to the non-ionized ones. Yet, if initial concentration of acid, cACID, is large enough, concentration of protons obtained from the ionization of the acid (also x) will be significantly higher than the one obtained from ionization of water. Accordingly, protons obtained from water ionization can be ignored during the calculation. CH3 COOHðaqÞ 1Þ INITIAL STATE cACID 2Þ EQUILIBRIUM cACID − x  cACID

⇄

Hð+aqÞ 10 − 7 M −7 10 M + x  x

+

CH3 COOð−aqÞ 0M x

It is important to notice that equal concentration of proton and the conjugate base originates from ionization of the acid. Therefore ionization constant can be written as: ½H + 
½CH3 COO −  ½H +   ½CH3 COOH cACID

2

KA =

(3:24)

Equation (3.24) can be rearranged as follows: ½H +  =

pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi KA
cACID

(3:25) 1

− log½H +  = − log ðKA
cACID Þ2

(3:26)

This provides, finally, the general expression for calculation of pH-value of weak acid: 1 1 pH =
pKA −
log cACID 2 2

(3:27)

Sometimes, in cases of not so weak or much diluted acids, the concentration of ionized molecules of acid cannot be neglected. For such cases, quadratic equation instead of eq. (3.24) is recommended: KA =

x2 cACID − x

x2 + KA
x − KA
cACID = 0

(3:28) (3:29)

Every quadratic equation, from mathematical point of view, has two solutions: one positive and the other negative. Positive solutions should be taken in consideration for this specific case since concentration cannot have negative value:

x=

− KA +

qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi KA2 − 4
1
ð − KA
cACID Þ 2
1

(3:30)

54

3 Environmental Chemistry

i. e.:

½H +  =

− KA +

qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi KA2 + 4
KA
cACID

(3:31)

2

Many acids have more than one proton bounded. Such acids are called polyprotic acids. One of the well-known polyprotic acids is phosphoric acid, H3PO4. This acid is ionizing in three steps and each step is characterized by its own equilibrium constant (Table 3.1). Table 3.1: Ionization steps of phosphoric acid [1]. Reaction of ionization H3 PO4ðaqÞ ⇄ Hð+lÞ + H2 PO4−ðaqÞ H2 PO4−ðaqÞ ⇄ Hð+lÞ + HPO24ð−aqÞ HPO24ð−aqÞ ⇄ Hð+lÞ + PO34ð−aqÞ

Ionization constant   ½H + 
H2 PO4− KA1 = = 7.1
10 − 3 M ½H3 PO4    ½H + 
HPO24 −   KA2 = = 6.3
10 − 8 M H2 PO4−   ½H + 
PO34 −  = 4.2
10 − 13 M KA3 =  HPO24 −

pKAvalue 2.1 7.2

12.4

The first ionization step generates significantly higher concentration of protons then the remaining two steps, according to ionization constants. Therefore pH-value of solution that contains phosphoric acid can be calculated according to eq. (3.27) or (3.32), with appliance of appropriate ionization constant. Ions H2PO4– and HPO42– are amphoteric substances, while PO43– is pure base.

Examples for exercise Example 3.1. What is the pH value of 10 mM water solution of nitric acid? Nitric acid is a strong acid which ionizes completely in water (100 %). HNO3ðaqÞ ! Hð+aqÞ + NO3−ðaqÞ Therefore, in 10 mM solution of nitric acid, concentration of H+ ions that originate from HNO3 is 10 mM, i. e. 10–2 M. (It was said before that concentration values used in calculation of pH must be expressed as mol/L.) This concentration is much higher than concentration of protons that originate from autoionization of water (10–2 M ≪ 10–7 M). Thus, concentration of protons from the autoionization can be neglected while calculating pH. The calculation is performed according the eq. (3.23): pH = − log½H +  = − log cðHNO3 Þ = − log 10 − 2 = 2

3.6 Strong and weak bases

55

Example 3.2. What is the pH of 0.01 M water solution of hydrofluoric acid? KA = 6.6
10 − 4 M Hydrofluoric acid ionizes in water according the equation: HFðaqÞ ⇄ Hð+aqÞ + Fð−aqÞ It is a weak acid that ionizes only partially. This can be concluded from value of the acid ionization constant. Yet, the concentration of acid is high enough and allows us to neglect protons from water while calculating pH. Therefore, pH value can be calculated according to eq. (3.27): pH =

1 1
pKA −
log cðHFÞ 2 2

  pKA = − log KA = − log 6.6
10 − 4 = 3.18 pH =

1 1
3.18 −
log 0.01 = 2.59 2 2

Example 3.3. What is the pH of 0.1 M water solution of carbonic acid? KA1 = 4.2
10 − 7 M, KA2 = 4.8
10 − 11 M Carbonic acid is a weak polyprotic acid that ionizes in water solutions in two further steps: STEP ONE:

H2 CO3ðaqÞ ⇄ Hð+aqÞ + HCO3−ðaqÞ

STEP TWO:

HCO3−ðaqÞ ⇄ Hð+aqÞ + CO23ð−aqÞ

Acid ionization constant for the first step is approximately 104 times higher than the one for the second step. Accordingly, the first step will generate significantly higher amount of protons so the second step can be omitted from the pH calculation. Thus, pH can be calculated according to eq. (3.27) but counting only first ionization step: 1 1
pKA1 −
log cðH2 CO3 Þ 2 2   pKA1 = − log KA1 = − log 4.2
10 − 7 = 6.38

pH =

pH =

1 1
6.38 −
log 0.1 = 3.69 2 2

3.6 Strong and weak bases Definition of strong and weak bases is analogous to those of strong and weak acids. Accordingly, the expression for pH-value for solution of a strong base, for example NaOH, can be derived as follows:

56

3 Environmental Chemistry

NaOHðaqÞ 1Þ INITIAL STATE cBASE 2Þ EQUILIBRIUM 0

!

Nað+aqÞ 0M cBASE

+ 10 − 7

OHð−aqÞ 10 − 7 M M + cBASE  cBASE

½OH −  = cBASE pOH = − log½OH −  = − log cBASE pH = pKW − pOH This leads to a general pH expression for solution of a strong base: pH = 14 + log cBASE

(3:32)

Calculation is more complicated in case of a weak base, like ammonium hydroxide: NH4OH. NH4 OHðaqÞ 1Þ INITIAL STATE cBASE 2Þ EQUILIBRIUM cBASE − x  cBASE

⇄

NH4+ðaqÞ 0M x

OHð−aqÞ 10 − 7 M −7 10 M + x  x

+

Mark x represents concentration of ionized molecules of base after equilibrium is reached. A general form for pH calculation can be obtained in a similar way as for weak acids:   NH4+
½OH −  ½OH − 2 = KB = ½NH4 OH cBASE

(3:33)

 KW = KA ½H +  =

 KW 2 ½H +  cBASE

rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi 1 KW
KA
cBASE

 − log½H +  = − log KW
KA


pH = 7 +

(3:34)

(3:35)

1 cBASE

1 1
pKA +
log cBASE 2 2

1

2

(3:36)

(3:37)

KA represents, in this specific case, ionization constant of NH4+, which is conjugate acid of base NH4OH. Of course, quadratic equation has to be solved for cases when x is not negligible in comparison with the cBASE:

3.6 Strong and weak bases

KB =

  NH4+
½OH −  x2 = ½NH4 OH cBASE − x

½OH −  =

− KB +

qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi KB2 + 4
KB
cBASE 2

57

(3:38)

(3:39)

Examples for exercise Example 3.4. What is the pH value of 0.02 M water solution of ammonium hydroxide? KB = 1.8
10 − 5 M Ammonium hydroxide is a weak base which ionizes partially in water: NH4 OHðaqÞ ⇄ NH4+ðaqÞ + OHð−aqÞ Thus, pH is calculated according the eq. (3.37):

pH = 7 +

1 1
pKA +
log cðNH4 OHÞ 2 2

Ionization constant of conjugate acid NH4+ is required for solving the previous equation. Therefore, eq. (3.22) will be applied:   pKB = − log KB = − log 1.8
10 − 5 = 4.74 pKA = pKW − pKB = 14.00 − pKB = 14.00 − 4.74 = 9.26 And the final step is: pH = 7 +

1 1
9.26 +
log 0.02 = 10.78 2 2

Example 3.5. What is the pH value of 0.15 M water solution of methylamine? KB = 5.0
10 − 4 M Methylamine is also a weak base. When dissolved in water, it reacts with the solvent’s molecules according the reaction: CH3 NH2ðaqÞ + H2 OðlÞ ⇄ CH3 NH3+ðaqÞ + OHð−aqÞ Calculation is similar as in previous example:

58

3 Environmental Chemistry

  pKB = − log KB = − log 5.0
10 − 4 = 3.30 pKA = pKW − pKB = 14 − pKB = 14 − 3.30 = 10.70

pH = 7 +

1 1 1 1
pKA +
log cðCH3 NH2 Þ = 7 +
10.70 +
log 0.15 = 11.94 2 2 2 2

3.7 Hydrolysis of salts Sometimes water solutions become acidic or basic after dissolution of a salt. Yet, in some cases the solutions remain neutral. How can salts influence pHvalue of the solutions? The answer lies in a phenomenon called hydrolysis. The term is derived from Greek words hydro, meaning water, and lysis, meaning breaking or solving. It is well known that chemical reaction between acidic and basic reactants generates salt and water. This reaction is called neutralization. Salt is consisted of conjugate base of the acidic reactant, and conjugate acid of the basic reactant. During dissolution process, salt completely or partially dissociates, releasing thus these conjugate components into the solvent. For example: H2 O

NaClðsÞ ! Nað+aqÞ + Clð−aqÞ

(3:40)

Hydrolysis is a reaction somehow opposite to neutralization: some of the ions released by salt dissociation can react with water, producing thus acidic compounds, basic compounds or both. It was said in chapter 5 that conjugate base can react with water, producing hydroxide ion and related weak acid (see eq. (3.17)). The same situation is with conjugate acids which in reaction with water produce weak base and proton. Yet, it is important to say that hydrolysis will not occur in cases when conjugate base or conjugate acid originate from strong acid or strong base, respectively. So the salt NaCl from eq. (3.40) originates from strong acid HCl and strong base NaOH. Dissolving of this salt in water will not initiate hydrolysis and pH-value of the solution remains neutral. Let’s discuss salt ammonium chloride, NH4Cl. This salt dissociates completely while dissolved in water, producing ammonium and chloride ions: H2 O

NH4 ClðsÞ ! NH4+ðaqÞ + Clð−aqÞ

(3:41)

Ammonium ion originates from weak ammonium hydroxide and therefore will partially react with water. Chloride originates from strong hydrochloric acid and will not hydrolyze.

3.7 Hydrolysis of salts

NH4+ðaqÞ 1Þ INITIAL STATE cSALT 2Þ EQUILIBRIUM cSALT − x  cSALT

+

H2 OðlÞ

⇄

59

NH4 OHðaqÞ + Hð+aqÞ 0M 10 − 7 M −7 x 10 M + x  x

Concentration of ammonium ion in initial state equals concentration of dissolved salt what is consequence of full dissociation of salt in water. Concentration of ammonium ions that will react with water in equilibrium state is defined by the size of constant of hydrolysis, KH: KH =

½H + 
½NH4 OH   NH4+

(3:42)

Let’s expand the fraction from eq. (3.42) by multiplying and dividing it with the equilibrium concentration of hydroxide ion. KH =

½H + 
½NH4 OH ½OH −   
½OH −  NH4+

(3:43)

Incorporation of eqs (3.10), (3.20) and (3.33) in eq. (3.43) confirms that constant of hydrolysis for ammonium chloride is actually ionization constant of acid NH4+. KH =

KW = KA KB

(3:44)

Ammonium chloride in water solution acts like a weak acid. Therefore, the expression for pH-value of weak acids (3.28) can be applied for such solution. A short derivation from eqs (3.42) and (3.44) will be presented in order to prove this statement. It is assumed that equilibrium concentration of ammonium equals initial concentration of the salt, and that equilibrium concentration of hydronium ions is equal to equilibrium concentration of ammonium hydroxide. 2

KA =

(3:45)

pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi KA
cSALT

(3:46)

1 1
pKA −
log cSALT 2 2

(3:47)

½H +  =

pH =

½H +  cSALT

The analogy with general expression for calculation of pH-value of weak acids (eq. (3.27)) is clearly evident.

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3 Environmental Chemistry

The salt sodium acetate dissociates completely in water solution: H2 O

CH3 COONaðsÞ ! Nað+aqÞ + CH3 COOð−aqÞ

(3:48)

The salt consists of sodium cation, which originates from strong NaOH base, and acetate anion from weak acetic acid. Therefore, only acetate anion does hydrolysis in water solutions. CH3 COOð−aqÞ 1Þ INITIAL STATE cSALT 2Þ EQUILIBRIUM cSALT − x  cSALT

+

⇄

H2 OðlÞ

CH3 COOHðaqÞ + OHð−aqÞ 0M 10 − 7 M −7 x 10 M + x  x

Concentration of acetate ion in initial state equals concentration of dissolved salt. Since hydrolysis occurs on anion only, the salt acts like weak base: KB =

½HAc
½OH −  ½OH − 2  ½Ac −  cSALT KW ðKW ½H + Þ = KA cSALT

(3:49)

2

rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi 1 ½H  = KW
KA
cSALT +

1 1 pH = 7 +
pKA +
log cSALT 2 2

(3:50)

(3:51)

(3:52)

Once again, the analogy with expression for calculation of pH value of weak base (eq. (3.37)) is present. Ammonium acetate is an example for amphoteric salt. H2 O

CH3 COONH4ðsÞ ! NH4+ðaqÞ + CH3 COOð−aqÞ

(3:53)

NH4+ðaqÞ + CH3 COOð−aqÞ + H2 OðlÞ ⇄ NH4 OHðaqÞ + CH3 COOHðaqÞ

(3:54)

The salt is comprised from ammonium and acetate ion. The cation is a weak acid, while the anion originates from weak acetic acid. Ionization constants that relate these two acids are required for calculation of pH-value of the solution. The general expression is: pH =

1
ðpKA1 + pKA2 Þ 2

(3:55)

3.7 Hydrolysis of salts

61

Examples for exercise Example 3.6. What is the pH value of 0.17 M solution of ammonium nitrate? K ðNH4 + Þ = 5.6
10 − 10 M Ammonium nitrate dissociates completely in water solutions: H2 O

NH4 NO3ðsÞ ! NH4+ðaqÞ + NO3−ðaqÞ Only one of the ions obtained by dissociation has ability to react with water, i. e. ability to do hydrolysis. It is ammonium ion since its origin is the weak base NH4OH. NH4+ðaqÞ + H2 OðlÞ ⇄ NH4 OHðaqÞ + Hð+aqÞ Obviously, this salt acts like weak acid so eq. (3.47) can be used for calculation of pH value of the solution:       pKA = pK NH4+ = − log K NH4+ = − log 5.6
10 − 10 = 9.25 pH =

1 1 1 1
pKA −
log cðNH4 NO3 Þ =
9.25 −
log 0.17 = 4.24 2 2 2 2

Example 3.7. 0.3100 g of sodium nitrite, NaNO2, was dissolved in 1 L of distilled water. What is the pH of the solution? K ðHNO2 Þ = 7.2
10 − 4 M Primary, it is necessary to determine molar concentration, c, of NaNO2 in the solution. The amount of dissolved sodium nitrate expressed in mols, n, can be obtained from a ratio of the salt’s dissolved mass, m, and its molar mass, M: nðNaNO2 Þ =

mðNaNO2 Þ 0.3100 g = 4.45
10 − 3 mol = MðNaNO2 Þ 69.00 g mol

Now it is easy to calculate the molar concentration knowing that NaNO2 is dissolved in 1 L, i. e. 1 dm3, of water. cðNaNO2 Þ =

nðNaNO2 Þ 4.45
10 − 3 mol = = 4.45
10 − 3 M VWATER 1 dm3

Sodium nitrite is a salt that also dissociate completely in water: H2 O

NaNO2ðsÞ ! Nað+aqÞ + NO2−ðaqÞ The obtained nitrite ion comes from a weak acid HNO2 and accordingly will react with water. NO2−ðaqÞ + H2 OðlÞ ⇄ HNO2ðaqÞ + OHð−aqÞ

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3 Environmental Chemistry

Sodium ion comes from a strong base NaOH and accordingly will not hydrolyze. Therefore, sodium nitrite in water media acts like weak base, and eq. (3.52) can be applied for calculation of pH value:   pKA = − log K ðHNO2 Þ = − log 7.2
10 − 4 = 3.14 pH = 7 +

  1 1 1 1
pKA +
log cðNaNO2 Þ = 7 +
3.14 +
log 4.45
10 − 3 = 7.40 2 2 2 2

Example 3.8. 100 mL of 0.300 M solution of HF was added into 300 mL of 0.100 M ammonium hydroxide. What is the pH value of such obtained solution? K ðHFÞ = 6.6
10 − 4 M, K ðNH4 + Þ = 5.6
10 − 10 M Total volume of the mixed solutions, VTOTAL, is sum of volumes of the separate solutions, VHF and VNH4 OH : VTOTAL = VHF + VNH4 OH = 100 mL + 300 mL = 400 mL = 0.400 dm3 Addition of 100 mL of hydrofluoric acid into 300 mL of ammonium hydroxide solution is causing dilution of both solutions and, accordingly, concentrations of both chemicals: HF and NH4OH, are changed. New molar concentrations are: VHF 100 mL = 0.300 M
= 0.075 M VTOTAL 400 mL VNH4 OH 300 mL = 0.100 M
= 0.075 M cðNH4 OHÞNEW = cðNH4 OHÞOLD
VTOTAL 400 mL cðHFÞNEW = cðHFÞOLD


Addition of hydrofluoric acid into ammonium hydroxide solution is also causing the neutralization: HFðaqÞ 1Þ INITIAL STATE 2Þ REACTION END

+

NH4 OHðaqÞ

!

NH4+ðaqÞ

+

Fð−aqÞ

0.075 M

0.075 M

0M

0M

0M

0M

0.075 M

0.075 M

+

H2 OðlÞ

Stoichiometrically equivalent amounts of acid and base are joined together in this specific case. So the reactants react completely and only the resulting NH4F salt and water remain at the reaction end. NH4F salt is completely dissociated in water solutions and exists only as separated ions NH4+ and F–. Both of these ions have the ability to do hydrolysis, so this is an amphoteric salt. pH value of the salt solution is calculating from the eq. (3.55): 1
ðpKA1 + pKA2 Þ 2   pKA1 = pK ðHFÞ = − log K ðHFÞ = − log 6.6
10 − 4 = 3.18  +  +   pKA2 = pK NH4 = − log K NH4 = − log 5.6
10 − 10 = 9.25 pH =

pH =

1 ð3.18 + 9.25Þ = 6.21 2

3.8 Buffers

63

3.8 Buffers Some solutions show significant ability to resist the change of pH-value upon the addition of acidic or basic components. These solutions are called buffers. Buffer solutions can be combination of a weak acid and its salt (e. g. CH3COOH/CH3COONa), a weak base and its salt (e. g. NH4OH/NH4Cl), or even two salts of which first salt must act like weak base or weak acid while the other salt must be derived from the first one (e. g. NaHCO3/Na2CO3). How is buffer capable to resist the change of pH-value? Let’s take CH3COOH/CH3COONa buffer for example. Sodium acetate is completely dissociated in water solution according to eq. (3.48). Therefore, equilibrium involves further species: Nað+aqÞ + CH3 COOð−aqÞ + CH3 COOHðaqÞ ⇄ Nað+aqÞ + CH3 COOð−aqÞ + Hð+aqÞ + CH3 COOð−aqÞ from CH3 COONa

from CH3 COONa

from CH3 COOH

(3:56) The acetate ions in solution mostly originate from the salt. cðCH3 COO − Þfrom CH3 COONa  cðCH3 COO − Þfrom CH3 COOH

(3:57)

Adding an additional amount of protons into buffer solution will not cause significant change of the pH-value since added protons will instantly react with acetate ions, already present in the solution, thus forming poorly dissociated acetic acid: Hð+aqÞ + CH3 COOð−aqÞ ⇄ CH3 COOHðaqÞ

(3:58)

Addition of hydroxide ions will not significantly change pH-value of buffer solutions, also. Added hydroxide ions are instantly reacting with present protons, forming poorly dissociated water molecules (eq. (3.8)). This reaction removes protons from equilibrium described by eq. (3.56). Yet, there is a large reserve of acetic-acid molecules that are not ionized (left side of the eq. (3.57)). These molecules are instantly compensating lack of protons by additional ionization. The similar situation is happening in case of basic buffer NH4OH/NH4Cl. Equilibrium in the buffer solution can be described as follows: NH4+ðaqÞ from NH4 Cl

+ Clð−aqÞ + NH4 OHðaqÞ ⇄ NH4+ðaqÞ + Clð−aqÞ + NH4+ðaqÞ + OHð−aqÞ from NH4 Cl

(3:59)

from NH4 OH

There is a large amount of ammonium ions in solution that mostly originates from the salt.   c NH4+ from NH

4 Cl

   c NH4+ from NH

4 OH

(3:60)

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3 Environmental Chemistry

Potentially added hydroxide ions instantly react with large amount of available ammonium ions, forming poorly dissociated molecules of ammonium hydroxide and thus pH-value of the solution remains preserved. NH4+ðaqÞ + OHð−aqÞ ⇄ NH4 OHðaqÞ

(3:61)

Added protons will react with hydroxide ions thus forming water (eq. (3.8)) as a weak electrolyte. Removal of hydroxide ions from equilibrium (3.60) will provoke further ionization of large amount of still non-ionized molecules of ammonium hydroxide and the pH-value of solution will maintain unchanged. Equilibrium in the discussed NH4OH/NH4Cl buffer system is described by ionization constant of ammonium hydroxide:   NH4+
½OH −  KB = ½NH4 OH

(3:62)

This equation can be easily transformed into general equation for buffer solutions, known as the Henderson–Hasselbalch equation (eq. (3.66)). 

 Kw NH4+
+ Kw ½H  = KA ½NH4 OH ½H +  = KA


  NH4+ ½NH4 OH

½NH4 OH  pH = pKA + log  NH4+ pH = pKA + log

cBASIC FORM cACIDIC FORM

(3:63)

(3:64)

(3:65)

(3:66)

According to the Henderson–Hasselbalch equation, pH of a buffer is determined by two factors: acid ionization constant of related acid and the ratio of equilibrium concentrations of basic and acidic component from the buffer solution. Be aware that buffer solutions have their buffer capacity and cannot resist indefinite addition of acid or base substances.

Examples for exercise Example 3.9. 500 mg of sodium nitrite, NaNO2, was added in 500 mL of 0.1 M nitrous acid, HNO2. What is the pH of the solution?

3.8 Buffers

65

K ðHNO2 Þ = 7.2
10 − 4 M Molar concentration of added sodium nitrite, c, can be calculated in following way: nðNaNO2 Þ =

mðNaNO2 Þ 0.500 g = 7.25
10 − 3 mol = MðNaNO2 Þ 69.00 g mol

cðNaNO2 Þ =

nðNaNO2 Þ 7.25
10 − 3 mol = = 1.45
10 − 2 M VNITROUS ACID 0.5 dm3 SOLUTION

Calculation of pH is done using eq. (3.66): pH = pKA + log

cBASIC FORM cACIDIC FORM

  pKA = − log K ðHNO2 Þ = − log 7.2
10 − 4 = 3.14 pH = pKA + log

cðNaNO2 Þ 1.45
10 − 2 = 3.14 + log 0.1 = 2.30 cðHNO2 Þ

Example 3.10. 700 mg of sodium phosphate (Na3PO4) was dissolved in 1 L of 1.0
10 − 3M phosphoric acid, H3PO4. What is the pH value of such obtained solution? KA1 = 7.1
10 − 3 M, KA2 = 6.3
10 − 8 M, KA3 = 4.2
10 − 11 M The first step is to calculate molar concentration of added sodium phosphate: nðNa3 PO4 Þ =

cðNa3 PO4 Þ =

mðNa3 PO4 Þ 0.700 g = 4.27
10 − 3 mol = MðNa3 PO4 Þ 163.94 g mol nðNa3 PO4 Þ VPHOSPHORIC ACID

=

4.27
10 − 3 mol = 4.27
10 − 3 M 1 dm3

SOLUTION

Sodium phosphate dissociates completely in water solutions. Thus, concentration of phosphate anion equals concentration of the salt:   c PO34 − = cðNa3 PO4 Þ = 4.27
10 − 3 M Na3PO4 acts like base in water solutions due to the hydrolysis of phosphate anion: PO34ð−aqÞ + H2 OðlÞ ⇄ HPO24ð−aqÞ + OHð−aqÞ Therefore, if Na3PO4 is added into acidic solution, like water solution of phosphoric acid is, the neutralization will happen:

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3 Environmental Chemistry

1Þ INITIAL STATE 2Þ END OF FIRST NEUTRALIZATION STEP

H3 PO4 ðaqÞ 1.0
10 − 3 M

+

PO34ð−aqÞ 4.3
10 − 3 M

!

3.3
10 − 3 M

0M

H2 PO4−ðaqÞ 0M

+

1.0
10 − 3 M

HPO24ð−aqÞ 0M 1.0
10 − 3 M

There is more than one neutralization step in this specific solution. The first neutralization step includes reaction between phosphoric acid and phosphate ion. Phosphoric acid is the limiting reactant in this case and therefore the reaction is happening until practically all phosphoric acid reacts with phosphate ions. The reaction results with two products: H2PO4– and HPO42–, both in concentrations equal to initial concentration of the limiting reactant. Concentration of the remaining phosphate ions is the difference between initial concentration of phosphate ions and initial concentration of phosphoric acid. So, three ionization forms of phosphoric acid are present in the solution at the end of the first neutralization step: H2PO4–, HPO42–, and PO43–. An additional neutralization will happen between the remaining phosphate ions and dihydrogen phosphate ion: H2 PO4−ðaqÞ 1Þ END OF FIRST NEUTRALIZATION STEP 2Þ END OF SECOND NEUTRALIZATION STEP

+

PO34ð−aqÞ

! HPO24ð−aqÞ

1.0
10 − 3 M

3.3
10 − 3 M

1.0
10 − 3 M

0M

2.3
10 − 3 M

2.0
10 − 3 M

The limiting reactant in this reaction is H2PO4–. Only two ionic forms of the phosphoric acid remain in the solution at the end of the reaction: HPO42–, and PO43–. Further neutralization is impossible, since these two ions form the equilibrium according the reaction: HPO24ð−aqÞ ⇄ PO34ð−aqÞ + Hð+aqÞ This presents a buffer solution so pH can be calculated according the eq. (3.66): pH = pKA + log

cBASIC FORM cACIDIC FORM

Acidic form of the buffer is HPO42–, while PO43– is the basic one. KA3 will be used for calculation of pKA value, since it relates the existing equilibria. Concentration of phosphate ions, at the end of the reaction, is reduced for the initial concentration of dihydrogen phosphate ions, while the concentration of hydrogen phosphate ions in enlarged for the same amount. pKA3 = − log pKA3 = − log 4.2
10 − 11 = 10.38   c PO34 − 2.3
10 − 3  = 10.38 + log = 10.44 pH = pKA3 + log  2− 2.0
10 − 3 c HPO4

3.9 Reactions of complexation Chemical complex consists of a central atom surrounded by a certain number of ligands [7]. Ligands are anions or neutral molecules that contain one or more

3.9 Reactions of complexation

67

electron-pairs which can be shared with the central atom. The sharing of the electrons is one-sided: the ligands are exclusively donors of the electrons and provide whole electron pair for the incurring bond with the central atom. In compliance, the central atom acts exclusively as acceptor of the electrons. The formed bond has both covalent and ionic character [8]. According to ligand field theory [9], the electrostatic field of present ligands causes splitting in the energy levels of the d-orbitals of central ion what results with stabilization of the complex compound. Let’s take Cd(CN)42– complex for further consideration. This complex is formed by bonding four cyanide ligands on Cd2+ central ion: 2− + − Cd2ðaq Þ + 4CNðaqÞ ⇄ CdðCNÞ4ðaqÞ

(3:67)

The equilibrium can be described using the stability constant of complex compound, KST (sometimes also called the complex formation constant, KF): h i CdðCNÞ24 − KST =  2 +  Cd
½CN − 4

(3:68)

or the instability constant, KINST, that relates the opposite reaction, i. e. disintegration of the complex:  2+  Cd
½CN − 4 i KINST = h CdðCNÞ24 −

(3:69)

It is obvious that stability and instability constants of complex compounds are reciprocal: KST =

1 KINST

pKST = − pKINST

(3:70)

(3:71)

Equation (3.67) is just a simplified way to present real path of formation of Cd(CN)42– complex. In real systems, like water solution, Cd2+ ions tend to form stable complexes. Water molecules are the only available ligands. Therefore, in water solutions, Cd2+ ions are present in Cd(H2O)42+ form and formation of Cd(CN)42– complex is practically reaction of ligand-exchange. This exchange performs stepwise as presented in Table 3.2. The constant for cumulative equation from Table 3.2 is obtained by multiplying equilibrium constants of each exchange step:

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3 Environmental Chemistry

Table 3.2: Stepwise replacement of H2O ligands by CN– ions in formation of Cd(CN)42– complex. Replacement steps CdðH2 OÞ24 +

−

Equilibrium constant   CdðH2 OÞ3 ðCNÞ + KST1 = ½CdðH2 OÞ24 + 
½CN −    CdðH2 OÞ2 ðCNÞ2 KST2 = + ½CdðH2 OÞ3 ðCNÞ 
½CN −    CdðH2 OÞðCNÞ3− KST3 = ½CdðH2 OÞ2 ðCNÞ2 
½CN − 

+

+ CN ⇄ CdðH2 OÞ3 ðCNÞ + H2 O

CdðH2 OÞ3 ðCNÞ + + CN − ⇄ CdðH2 OÞ2 ðCNÞ2 + H2 O CdðH2 OÞ2 ðCNÞ2 + CN − ⇄ CdðH2 OÞðCNÞ3− + H2 O CdðH2 OÞðCNÞ3− + CN − ⇄ CdðCNÞ24 − + H2 O

KST4 =

½CdðCNÞ24 −  ½CdðH2 OÞðCNÞ3− 
½CN − 

h

i CdðCNÞ24 − i KST = KST1
KST2
KST3
KST4 = h CdðH2 OÞ24 +
½CN − 4

(3:72)

Complexes have different applications in environmental chemistry practice. Those of high stability can be used to improve solubility of highly insoluble minerals or to immobilize (mask) the trouble-making compounds in analytical matrices while performing chemical analysis. Also, transition metals form highly colorable complexes what is commonly used in qualitative or quantitative chemical analysis.

3.10 Redox reactions Chemical reactions that include change of oxidation state of reacting compounds, as a direct consequence of electron exchange, are called redox reactions. For example: + 4+ Hg22ð+aqÞ + Sn2ðaq Þ ⇄ 2HgðsÞ + SnðaqÞ

(3:73)

In the considered redox reaction, mercury changes its oxidation state from +1 into 0, and tin from +2 into +4. Each redox reaction is comprised of two half-reactions: the reaction of oxidation and the reduction. During oxidation process, reactant releases one or more electrons and accordingly increases its oxidation state. For considered example, it is further half-reaction: ð + 2Þ

ð + 4Þ

+ 4+ − Sn2ðaq Þ ⇄ SnðaqÞ + 2e

The reactant that is oxidized is called reducer or reducing agent.

(3:74)

3.10 Redox reactions

69

The opposite half-reaction in which reactant accepts one or more electrons and reduces its own oxidation state is called the reduction: ð + 1Þ

ð0Þ

Hg22ð+aqÞ + 2e − ⇄ 2HgðsÞ

(3:75)

The reactant that reduces its oxidation number and therefore oxidizes reactant from other half-reaction is called oxidant or oxidizing agent. Each of these half-reactions has its relative standard electrode potential, E0. The value of this physical-chemical property is commonly expressed considering reaction of the chemical reduction, and that will be the rule in this book also. Relative standard electrode potential is an electrode potential measured against reference electrode [10]. Commonly used reference electrode is standard hydrogen electrode which has for every temperature and under standard conditions nominated value of 0 V. Therefore, relative standard electrode potential for system described by eq. (3.75) is actually the potential difference between this system and system described by reaction: ð + 1Þ

ð0Þ

2Hð+aqÞ + 2e − ⇄ H2ðgÞ

(3:76)

Driving force for each redox system is redox potential of the system. Redox potential is difference between relative electrode-potentials of the reduction reaction and the oxidation reaction. Relative electrode potential of some half-system depends on relative standard electrode potential, number of exchanged electrons (n) and concentration of oxidized and reduced form of the agent. The related mathematical expression is known as Nernst equation: E = E0 +

R
T cOXIDIZED FORM
ln cREDUCED FORM n
F

(3:77)

Fraction that multiplies logarithm in eq. (3.77) has two constants: constant R is universal gas constant with value 8.314 J/K mol, and F presents Faraday constant of 96485 C/mol. T is absolute temperature. Nernst equation can be simplified for room temperature condition (273.15 K): E = E0 +

0.059 V cOXIDIZED FORM
log cREDUCED FORM n

(3:78)

The concentration in Nernst equation will be replaced by partial pressure of the component (expressed in atmospheres; 1 atm = 101325 Pa) if the component is present in gas form. Also, concentration of pure solids is by default equal to 1 [1]. Nernst equation applied on system presented by reaction (3.75) is:

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3 Environmental Chemistry

0 ESn4 + =Sn2 + = ESn 4 + =Sn2 + +

0.059 V cðSn4 + Þ
log 2 cðSn2 + Þ

(3:79)

For some redox systems, relative electrode potential can be function of concentration of hydronium ion, i. e. pH-value of the solution. Namely, Nernst equation for system MnO4–/Mn2+ has following form: + MnO4−ðaqÞ + 8Hð+aqÞ + 5e − ⇄ Mn2ðaq Þ + 4H2 OðlÞ

0 EMnO − =Mn2 + = EMnO − =Mn2 + 4 4

  c MnO4−
c8 ðH + Þ 0.059 V +
log cðMn2 + Þ 5

(3:80)

(3:81)

The potential of this and similar systems can be, obviously, additionally altered by changing acidity of the solution. Which reactant will act like oxidant, and which one will be the reducer in some redox system? For the answer, one needs to compare relative electrode-potentials of both redox half-systems. Half-system with higher value of the relative electrode potential will be the oxidant. Problem 3.3. Compare values of relative standard electrode potentials and give answers on two questions: 1. Which system can oxidize all other systems from the Table 3.3? 2. Which system can reduce all other systems from the Table 3.3?

Among the presented systems, system H2O2/2H2O has highest value of relative standard electrode potential and therefore can oxidize all other systems from Table 3.3. Table 3.3: Relative standard electrode potentials of several reduction systems [1]. E0/V

Reaction of reduction

–0.41 –0.26

Cr3 + + e − ⇄ Cr2 + V3 + + e − ⇄ V2 + 2H + + 2e − ⇄ H2 I3− + 2e − ⇄ 3I −

0.00 0.54 0.77 0.91

Fe3 + + e − ⇄ Fe2 + 2Hg2 + + 2e − ⇄ Hg22 + Cr2 O27 − + 14H + + 6e − ⇄ 2Cr3 + + 7H2 O MnO4−

−

+ 8H + 5e ⇄ Mn + 4H2 O H2 O2 + 2H + + 2e − ⇄ 2H2 O +

2+

1.33 1.51 1.78

71

3.10 Redox reactions

Among the presented systems, system Cr3+/Cr2+ has lowest value of relative standard electrode potential and therefore it is capable to reduce all other systems from Table 3.3. Let’s discuss redox system composed of MnO4–/Mn2+ and Fe3+/Fe2+ half-systems. Suppose that concentrations of ionic forms are 1 M. According to data presented in Table 3.3, the oxidant will be permanganate ion, MnO4–, and the system will behave as follows: REDUCTION :

+ MnO4−ðaqÞ + 8Hð+aqÞ + 5e − ⇄ Mn2ðaq Þ + 4H2 OðlÞ

(3:82)

+ 3+ − Fe2ðaq Þ ⇄ FeðaqÞ + e

(3:83)

OXIDATION :

Five electrons are exchanged between these two half-systems. Therefore, eq. (3.83) has to be multiplied by 5 and then sum with eq. (3.82) to obtain cumulative chemical equation: + 2+ 3+ MnO4−ðaqÞ + 8Hð+aqÞ + 5Fe2ðaq Þ ⇄ MnðaqÞ + 4H2 OðlÞ + 5FeðaqÞ

(3:84)

Driving force of the system, ΔE, is defined as: ΔE = EMnO − =Mn2 + − EFe3 + =Fe2 + = 1.51 V − 0.77 V = 0.74 V 4

(3:85)

ΔE is biggest at initial state since the initial state is characterized by highest difference of the potentials. Concentration of permanganate ion will be dwindling during the process of electron exchange as well as the concentration of Fe2+ ion. At the same time concentrations of Mn2+ and Fe3+ ions will rise. Due to the concentration changes, and following the Nernst equation (eq. (3.78)), potential of system MnO4–/Mn2+ will decreasing while the one of Fe3+/Fe2+ system will increasing, causing diminishing of the driving force. Potentials of both halfsystems will become equal by reaching the equilibrium: EMnO − =Mn2 + = EFe3 + =Fe2 + 4

0 EMnO − =Mn2 + 4

(3:86)

  8 5 MnO4−
½H +  0.059 V 0.059 V ½Fe3 +  0 + + = E
log
log 3 + 2 + 5 Fe =Fe ½Mn2 +  5 5 ½Fe2 +  (3:87)

Let’s transfer the standard potentials on one side of the equation, and the logarithmic expressions on the other one.

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3 Environmental Chemistry

5

0 0 EMnO − =Mn2 + − EFe3 + =Fe2 + = 4

0.059 V ½Mn2 + 
½Fe3 + 
log   8 5 MnO4−
½H + 
½Fe2 + 5

(3:88)

It is easy to observe that expression inside logarithm in eq. (3.88) presents equilibrium constant of redox system from eq. (3.84): 5

½Mn2 + 
½Fe3 +  KRO =   8 MnO4−
½H + 
½Fe2 + 5

(3:89)

Therefore, general equation that relates equilibrium constant of some redox system with relative standard electrode potentials is: E10 − E20 =

0.059 V
log KRO n1
n2

(3:90)

System 1 from eq. (3.90) is system with higher value of relative electrode potential.

Examples for exercise Example 3.11. What is the potential of Pb2+/Pb system in solution containing 0.100 M of Pb2+ ions?   E 0 Pb2 + =Pb = − 0.126 V The related reaction is: + − Pb2ðaq Þ + 2e ⇄ PbðsÞ

Nernst equation for this reaction is: 0 EPb2 + =Pb = EPb 2 + =Pb +

  c Pb2 + 0.059 V
log cðPbÞ 2

Concentration of pure solid phase, like solid lead in this example, is by default equal to 1 [1]. This simplifies the equation: 0 EPb2 + =Pb = EPb 2 + =Pb +

  0.059 V
log c Pb2 + 2

Finally, the potential is calculated as follows:

EPb2 + =Pb = − 0.126 V +

0.059 V log 0.100 = − 0.156 V 2

3.11 Solubility of minerals

73

Example 3.12. What is the value of equilibrium constant for the following redox system? − + Cr2 O27ð−aqÞ + 3ClO3−ðaqÞ + 8Hð+aqÞ ⇄ 2Cr3ðaq Þ + 3ClO4ðaqÞ + 4H2 OðlÞ

  E 0 Cr2 O7 2 − =Cr3 + = 1.333 V, E 0 ðClO4 − =ClO3 − Þ = 1.189 V The equilibrium constant for the given system is defined as follows: 3 2  ½Cr3 + 
ClO4− KRO =    3 8 Cr2 O27 −
ClO3−
½H +  Equation (3.90) will provide the value of the constant: 0.059 V
log KRO EXCHANGED ELECTRONS     0.059 V E 0 Cr2 O27 − =Cr3 + − E 0 ClO4− =ClO3− =
log KRO 6

E10 − E20 =

n

0.059 V
log KRO 6 log KRO = 14.64

1.333 V − 1.189 V =

KRO = 4.4
1014 M − 7

3.11 Solubility of minerals The emergence of solid phase from water solution, i. e. the precipitation, is important phenomena in environmental chemistry since it is commonly used in many processes relating water treatment. Dissolution of minerals is the opposite process that requires contact between mineral and water, i. e. the existence of boundary between solid and liquid phase. Minerals dissolved in water can change chemical characteristics of the water. Just remember the occurrence of hydrolysis (chapter 7). Maximal amount of solid that can be dissolved in certain volume of solvent at specified temperature is called solubility. Chemical reactions of dissolving/precipitation also tend to reach equilibrium state. The equilibrium is described by solubility product constant, KSP, sometimes simply called solubility product. The KSP is the product of the concentrations of ions obtained by dissolution of the mineral, with each ion concentration raised to a power equal to the coefficient of that ion in balanced equation for the solubility equilibrium. Concentration of solid phase is not taken in consideration when defining KSP. Taking FeCl3 salt as an example, the solubility product will be:

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3 Environmental Chemistry

  KSP = Fe3 +
½Cl − 3

(3:91)

since this salt dissolves according to further chemical equation: − + FeCl3ðsÞ ⇄ Fe3ðaq Þ + 3ClðaqÞ

(3:92)

There are three possible states of solution according to solubility of some precipitate: unsaturated, saturated and supersaturated solution. Unsaturated solution is the one in which the product of concentrations of ions that constitute precipitate (each ion concentration should be raised to a power equal to the ion’s stoichiometric coefficient from the solubility equation) is lower than related solubility product:   c Fe3 +
c3 ðCl − Þ < KSP

(3:93)

Any addition of new solid particles of FeCl3 into unsaturated solution will cause further dissolution of the salt, in order to reach the equilibrium. Solution becomes saturated in cases when the product of concentrations of ions reaches the value of solubility product. The equilibrium is established at this point, and the speeds of dissolving and precipitation became equal. Supersaturated solution is highly unstable since the product of concentrations of ions is higher than the solubility product. Precipitation occurs only in supersaturated solutions. Several effects, like nature of solvent and solute, temperature, common-ion effect, effect of complex formation, electrolyte effect, and pH-value of solution, have influence on solubility of minerals. These effects will be discussed in the following text. 3.11.1 Nature of solvent and solute Effect that nature of solvent has on solids solubility follows general rule: “like dissolves like”. This means that a solute will be dissolved best in a solvent that has chemical properties similar to the solute. The most important property is polarity. Therefore polar solvents are required to dissolve compounds with ionic characteristics, like salts [11]. For example, water is a polar solvent with partially negative charge on oxygen atom and partially positive charge on hydrogen atoms. Thus, ionic compounds like NaCl dissolve easily in water due to the attractive forces between positive Na+ ions and negatively charged part of water molecule, and, in the equivalent way, the attractions between Cl– and positively charged part of the water. On the other side, non-polar compound naphthalene is practically insoluble in water, but it is highly soluble in non-polar solvent like benzene.

3.11 Solubility of minerals

75

3.11.2 Temperature effect Temperature has dual effect on solubility of minerals: it affects equilibrium of the precipitation and the reaction rate. The solubility generally increases with rising of the temperature. Yet, it is important to say that for some very common environmental minerals, such as CaCO3, Ca3(PO4)2, CaSO4 and FePO4, the dissolution is exothermic process and accordingly, the exceptions were noticed [4]. These salts are practically insoluble in water and only very small concentrations of the ions that constitute these salts are present in water solution at room temperature. Yet, at higher temperature, due to the inverse solubility, even these small concentrations will be sufficient for further precipitation of the salt. This causes severe problems in processes using heat exchangers. Deposition of salt on the exchanger’s surface decreases the efficiency of the heat exchange. This is reason why water with high content of calcium ions usually needs a treatment. The treatment includes ion-exchange of calcium with sodium ions; the process is called water softening. The temperature effect on equilibrium is described by Van’t Hoff’s equation: ln

  K1 ΔH 0 1 1 = −
K2 R T2 T1

(3:94)

T1 and T2 are absolute temperatures, K1 and K2 equilibrium constants at the related temperatures, R ideal gas constant, and ΔH0 standard enthalpy change. 3.11.3 Common-ion effect Let’s take barium chromate to explain common-ion effect. Interactions between water molecules and the salt crystal are strong due to water polarity and ionic nature of bond between barium and chromate. Water molecules are pulling apart the ions from salt crystal and thus dissolving the salt. This can be described by simplified chemical reaction: 2− + BaCrO4ðsÞ ⇄ Ba2ðaq Þ + CrO4ðaqÞ

(3:95)

All dissolved BaCrO4 units are present in solution in form of solvated ions. The amounts of barium and chromate ions equal the amount of dissolved BaCrO4 units and for saturated solution these amounts are equal to the solubility of the salt.     sðBaCrO4 Þ = Ba2 + = CrO24 −

(3:96)

Solubility can be now easy calculated from known value of the solubility product:

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3 Environmental Chemistry

    KSP ðBaCrO4 Þ = Ba2 +
CrO24 −

sðBaCrO4 Þ =

pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi KSP ðBaCrO4 Þ

(3:97)

(3:98)

But, what happens with solubility of a mineral if one of the ions that form the mineral originates from some other chemical? Let’s imagine that someone disrupted the existed solubility equilibrium by adding extra amount of one of the precipitate ions, i. e. the common ion, for example chromate. Consequently, the reaction between barium and chromate ion will occur, according to Le Chatelier’s [12] principle. The reaction will occur in order to lower concentration of added chromate ions and thus reestablish the equilibrium (eq. (3.97)). So, the presence of chromate ions from some other source will cause inevitable decrease of concentration of barium ions. Since barium ions come exclusively from the salt, their concentration determines solubility of the salt. sðBaCrO4 Þ =

KSP ðBaCrO4 Þ   CrO24 −

(3:99)

The conclusion is that addition of common ion reduces solubility of salt. 3.11.4 Effect of complex formation Solubility of the minerals can be improved by addition of agent that form stable chemical complex with one of precipitate ions. AgCl is heavily insoluble salt which dissociates according to reaction: AgClðsÞ ⇄ Agð+aqÞ + Clð−aqÞ

(3:100)

Yet, in presence of ammonia, silver forms highly stable silver ammine complex (KST = 1.6·107 M): Agð+aqÞ + 2NH3ðaqÞ ⇄ AgðNH3 Þ2+ðaqÞ

(3:101)

This reaction practically is pulling silver ion out of reaction (100), causing further dissolution of the salt. More accurate statement is that there are two systems in solution that highly affect each other. Chemical reaction that describes integrated behavior of both systems can be obtained as sum of eqs. (3.100) and (3.101): AgClðsÞ + 2NH3ðaqÞ ⇄ AgðNH3 Þ2+ðaqÞ + Clð−aqÞ

(3:102)

3.11 Solubility of minerals

KR =

  AgðNH3 Þ2+
½Cl −  ½NH3 2

77

(3:103)

Analysis of expression for constant of the summary reaction, KR (eq. (3.103)), leads to general conclusion that addition of complexing agent increases solubility of the salt. The constant of the summary reaction, KR, can be calculated as a combination of the solubility product constant and the complex stability constant. KR for selected example is: 

 AgðNH3 Þ2+
½Cl −  ½Ag + 
= KST
KSP KR = ½Ag +  ½NH3 2

(3:104)

It is important to know that some common ions show different effects on mineral solubility, depending on their concentration. At low concentrations common-ion effect causes reduction of metal solubility while at higher concentrations common ions form complexes and consequently increase the solubility. 3.11.5 Electrolyte effect Solubility can be, like other chemical reactions, also affected with electrolyte effect. Ag2CrO4 dissolves according to reaction: Ag2 CrO4ðsÞ ⇄ 2Agð+aqÞ + CrO24ð−aqÞ

(3:105)

The activity, as more accurate approach, will be used instead molar concentration for calculation of solubility product during this specific discussion.   KSP ðAg2 CrO4 Þ = a2 ðAg + Þ
a CrO24 −

(3:106)

This equation can be modified taking in consideration the relation between activity and molar concentration (eq. (3.3)):     2 KSP ðAg2 CrO4 Þ = γ2 ðAg + Þ
½Ag + 
γ CrO24 −
CrO24 −

(3:107)

  KSP ðAg2 CrO4 Þ   = ½Ag + 2
CrO24 − γ2 ðAg + Þ
γ CrO24 −

(3:108)

Left side of eq. (3.108) has value higher than solubility product since activity coefficients are lower than 1 in concentrated electrolyte. This indicates that solubility of minerals increases with increase of the ionic strength (see chapter 3) [1].

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3 Environmental Chemistry

3.11.6 Effect of pH of the solution Solubility of minerals can be affected by change of solution’s pH-value. For example, in case of minerals which perform hydrolysis, like AgCN. This salt dissolves according to reaction: AgCNðsÞ ⇄ Agð+aqÞ + CNð−aqÞ

(3:109)

KSP ðAgCNÞ = 7.2
10 − 11 M2

(3:110)

One of the products of dissolving process is cyanide ion which, in reaction with hydronium ion, forms hydrogen cyanide, a very weak acid: Hð+aqÞ + CNð−aqÞ ⇄ HCNðaqÞ

(3:111)

KA = 2
10 − 9 M

(3:112)

Therefore, in acid environment, the summary reaction must be considered. The reaction can be obtained by adding together the eqs. (3.109) and (3.111): AgCNðsÞ + Hð+aqÞ ⇄ Agð+aqÞ + HCNðaqÞ

KR =

½Ag + 
½HCN s2 ðAgClÞ = ½H +  ½H + 

  qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi s AgClðsÞ = KR
½H + 

(3:113)

(3:114)

(3:115)

The equilibrium constant, KR, can be obtained as combination of the related solubility product and ionization constant of the acid: KR =

KSP ðAgCNÞ 7.2
10 − 11 M2 = 3.6
10 − 2 M = KA 2
10 − 9 M

(3:116)

An interesting example is aluminum hydroxide due to its amphoteric properties. Same effects like those presented for silver cyanide occurs for aluminum hydroxide in highly acid solutions. Aluminum hydroxide is dissolved in such environment and aluminum exists in forms of Al3+, AlOH2+ or Al(OH)2+ ions. Precipitation of aluminum hydroxide occurs at medium pH-values where addition of hydroxide ion decreases the solubility due to common-ion effect:

3.11 Solubility of minerals

79

+ − AlðOHÞ3ðsÞ ⇄ Al3ðaq Þ + 3OHðaqÞ

(3:117)

    KSP AlðOHÞ3 = Al3 +
½OH − 3

(3:118)

The concentration of Al3+ is in fact solubility of Al(OH)3:     KSP AlðOHÞ3 = s AlðOHÞ3
½OH − 3

(3:119)

To express the solubility, the eq. (3.119) can be rearranged as: 



s AlðOHÞ3 =

  KSP AlðOHÞ3 ½OH − 3

(3:120)

Since KSP is a constant, it is obvious from eq. (3.120) that the solubility of Al(OH)3 decreases with the increase of OH– concentration. But, with the further increase of OH– concentration (in basic environment) dissolving of aluminum hydroxide occurs as a result of complex formation: AlðOHÞ3ðsÞ + OHð−aqÞ ⇄ AlðOHÞ4−ðaqÞ

(3:121)

    AlðOHÞ4− s AlðOHÞ3 KR = = ½OH −  ½OH − 

(3:122)

  s AlðOHÞ3 = KR
½OH − 

(3:123)

Examples for exercise Example 3.13. What is the solubility of Hg2Cl2 in water? KSP ðHg2 Cl2 Þ = 1.3
10 − 18 M3 Solubility of Hg2Cl2 in water is only affected by polarity of water molecules. Therefore, it will be calculated from the expression for solubility product. Hg2 Cl2ðsÞ ⇄ Hg22ð+aqÞ + 2Clð−aqÞ   KSP ðHg2 Cl2 Þ = Hg22 +
½Cl − 2

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3 Environmental Chemistry

One diatomic mercury(I) ion (Hg22+) and two chloride ions arise from one particle of Hg2Cl2. Therefore solubility of the salt, s, equals the concentration of mercury(I) ions, i. e. the one half of the concentration of chloride ions. KSP ðHg2 Cl2 Þ = s
ð2sÞ2 = 4s3 This leads to the final solubility calculation: rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi KSP ðHg2 Cl2 Þ 1.3
10 − 18 M3 = 6.9
10 − 7 M s= 3 = 3 4 4 Example 3.14. What is the mass of silver bromide that can be dissolved in 1 L of 1.00 M solution of sodium thiosulfate?

KSP ðAgBrÞ = 5.2
10 − 13 M2 , KST AgðS2 O3 Þ2 3 − = 2.9
1013 M − 2 Silver bromide salt has very low value of the solubility product. Presence of thiosulfate ions in the solution will significantly increase its solubility due to the formation of quite stabile complex. Silver bromide dissociates according the reaction: AgBrðsÞ ⇄ Agð+aqÞ + Brð−aqÞ

KSP ðAgBrÞ = ½Ag + 
½Br −  The second important reaction that occurs in the solution is reaction of formation of Ag(S2O3)23– complex: Agð+aqÞ + 2S2 O23ð−aqÞ ⇄ AgðS2 O3 Þ32ð−aqÞ  3 −

= KST AgðS2 O3 Þ2

h i AgðS2 O3 Þ32 −  2 ½Ag + 
S2 O23 −

Sum of these two reactions gives the final reaction that controls the solubility of AgBr: AgBrðsÞ + 2S2 O23ð−aqÞ ⇄ AgðS2 O3 Þ32ð−aqÞ + Brð−aqÞ h i AgðS2 O3 Þ32 −
½Br −  KR =  2 S2 O23 − Value of the equilibrium constant of final reaction, KR, is currently unknown, but it is a combination of KSP(AgBr) and KST(Ag(S2O3)23–):

3.11 Solubility of minerals

81

h i  AgðS2 O3 Þ32 − 3 −

+ −
KSP ðAgBrÞ KR =  
½Ag 
½Br  = KST AgðS2 O3 Þ2 2− 2 + ½Ag 
S2 O3 KR = 2.9
1013 M − 2
5.2
10 − 13 M2 = 15.08 According the final reaction, dissolving of silver bromide in thiosulfate solution produces equal concentrations of bromide and thiosulfate complex. These concentrations match the concentration of the dissolved AgBr particles, i. e. they correspond to the solubility, s, of the AgBr: s2 ðAgBrÞ KR =  2 S2 O23 − Concentration of thiosulfate ions equals the concentration of sodium thiosulfate, since sodium thiosulfate dissociates completely in water solutions. This information leads to the final calculation for solubility: sðAgBrÞ =

qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi  2 KR
S2 O23 − = 15.08
ð1.00 MÞ2 = 3.88 M

Example 3.15. What is the solubility of Ni(OH)2 in water solution that has pH = 8.5?   KSP NiðOHÞ2 = 2.0
10 − 15 M3 Nickel hydroxide forms the following equilibrium in water solutions: + − NiðOHÞ2ðsÞ ⇄ Ni2ðaq Þ + 2OHðaqÞ

    KSP NiðOHÞ2 = Ni2 +
½OH − 2 The presented water solution is slightly basic, meaning that this solution has an elevated concentration of hydroxide ions. The hydroxide concentration is known from the solution’s pH value. pOH = 14 − pH = 14 − 8.5 = 5.5 pOH = − log½OH −  ½OH −  = 10 − pOH = 10 − 5.5 = 3.2
10 − 6 M Dissolution of nickel hydroxide in basic solutions is influenced by the common ion effect. Therefore, concentration of the dissolved Ni(OH)2 is equal to the concentration of nickel ions.     KSP NiðOHÞ2 = s NiðOHÞ2
½OH − 2     KSP NiðOHÞ2 2.0
10 − 15 M3 −4 s NiðOHÞ2 = = 2 = 1.9
10 M 2 ½OH −  3.2
10 − 6 M

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3 Environmental Chemistry

Example 3.16. 30 mL of 0.200 M water solution of Na2C2O4 was joined with 30 mL of saturated CaCO3 solution. Please calculate if CaC2O4 precipitate is present in such obtained solution. KSP ðCaCO3 Þ = 3.36
10 − 9 M2 , KST ðCaC2 O4 Þ = 2.32
10 − 9 M2 Total volume of the joined solution is 60 mL. Monitored precipitate in solution is CaC2O4, which incurs according the reaction: + 2− Ca2ðaq Þ + C2 O4ðaqÞ ⇄ CaC2 O4ðsÞ

    KSP ðCaC2 O4 Þ = Ca2 +
C2 O24 − Precipitation will occur if product of concentrations of ions that constitute CaC2O4 raised to a power equal to the ions’ stoichiometric coefficient from solubility reaction is higher than solubility product. Therefore, it is important to calculate these concentrations. Concentration of oxalate ion, C2O42–, equals the concentration of Na2C2O4 from the joined solution, since Na2C2O4 is totally dissociated in water solutions: cðNa2 C2 O4 ÞNEW = cðNa2 C2 O4 ÞOLD


VNa2 C2 O4 30 mL = 0.200 M
= 0.100 M VTOTAL 60 mL



c C2 O24ð−aqÞ = cðNa2 C2 O4 ÞNEW = 0.100 M

Concentration of calcium ion in saturated CaCO3 solution is determined from the related solubility product. + 2− CaCO3ðsÞ ⇄ Ca2ðaq Þ + CO3ðaqÞ

    KSP ðCaCO3 Þ = Ca2 +
CO23 − Also, concentration of calcium ions in this solution equals the concentration of carbonate ions, what provides easy calculation of the calcium concentration:   ½Ca2 +  = CO23 − 2

KSP ðCaCO3 Þ = ½Ca2 +  p ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi ffi pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi ½Ca2 +  = KSP ðCaCO3 Þ = 3.36
10 − 9 M2 = 5.80
10 − 5 M This concentration has been changed by dilution:     VCaCO3 30 mL = 5.80
10 − 5 M
= 2.90
10 − 5 M c Ca2 + NEW = c Ca2 + OLD
VTOTAL 60 mL Finally, the product of concentrations of calcium and oxalate ions is:

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References

    c Ca2 +
c CO23 − = 2.90
10 − 5 M
0.100 M = 2.90
10 − 6 M The obtained value is higher than solubility product of calcium oxalate. This indicates that calcium oxalate is precipitating from the solution.

3.12 Solubility of gases The solubility of gases in water decreases with increasing temperature. This is one of reasons why ecologists are concerned about increasing of thermal pollution of water. Among other bad effects, high temperatures of water cause hypoxia. This phenomenon refers to concentration of dissolved oxygen that is below acceptable level and consequently has devastating effect on water-ecosystems [11]. Pressure is the other important factor that has significant influence on solubility of gases. In cases with no chemical reaction, only partial pressure of the gas in surrounding atmosphere affects its solubility. This can be expressed by Henry’s law: si = KH, i
pi

(3:124)

Symbol si marks solubility of gas i, pi represents related partial pressure, and KH,i is Henry’s law constant applicable for particular gas i at specified temperature [13]. The existence of additional chemical reactions, like in case of ammonia or carbon dioxide which are reacting with water, may increase the solubility of gases. NH3ðgÞ ⇄ NH3ðaqÞ

(3:125)

NH3ðaqÞ + H2 OðlÞ ⇄ NH4+ðaqÞ + OHð−aqÞ

(3:126)

The summary reaction can be obtained from eqs (3.125) and (3.126): NH3ðgÞ + H2 OðlÞ ⇄ NH4+ðaqÞ + OHð−aqÞ

(3:127)

and is defined by equilibrium constant, KR:   NH4+
½OH −  KR = = KH
KB pðNH3 Þ

(3:128)

References [1] [2]

Skoog DA, West DM, Holler FJ, Crouch SR. Fundamentals of analytical chemistry. 9th ed. Belmont, CA: Brooks/Cole, 2014. Brönsted JN. EinigeBemerkungenüber den Begriff der Säuren und Basen. Recl Trav Chim Pays-B. 1923;42:718–28.

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[3] [4] [5]

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Lowry TM. The uniqueness of hydrogen. J Soc Chem Ind-L. 1923;42:43–47. Snoeyink VL, Jenkins D. Water chemistry. New York, NY: John Wiley & Sons, 1980. Evangelou VP. Environmental soil and water chemistry: principles and applications. New York, NY: John Wiley & Sons, 1998. [6] Myers RJ. One-hundred years of pH. J Chem Educ. 2010;87:30–32. [7] Vogel AI. Vogel’s textbook of macro and semimicro qualitative inorganic analysis. 5th ed. London, UK: Longman Group Limited, 1979. [8] Frenking G. Understanding the nature of the bonding in transition metal complexes: from Dewar’s molecular orbital model to an energy partitioning analysis of the metal–ligand bond. J Organomet Chem. 2001;635:9–23. [9] Ballhausen CJ. Introduction to Ligand field theory. New York, NY: McGraw-Hill, 1962. [10] Trassati S. The absolute electrode potential: an explanatory note (Recommendations 1986). Pure Appl Chem. 1986;58:955–66. [11] Chang R. Chemistry. 10th ed. New York, NY: McGraw Hill, 2000. [12] Harvey D. Modern analytical chemistry. Boston, MA: McGraw-Hill, 2000. [13] Manahan SE. Environmental chemistry. 7th ed. Boca Raton, FL: CRC Press LLC, 2000.

Felicita Briški and Marija Vuković Domanovac

4 Environmental microbiology Abstract: For most people, microorganisms are out of sight and therefore out of mind but they are large, extremely diverse group of organisms, they are everywhere and are the dominant form of life on planet Earth. Almost every surface is colonized by microorganisms, including our skin; however most of them are harmless to humans. Some microorganisms can live in boiling hot springs, whereas others form microbial communities in frozen sea ice. Among their many roles, microorganisms are necessary for biogeochemical cycling, soil fertility, decomposition of dead plants and animals and biodegradation of many complex organic compounds present in the environment. Environmental microbiology is concerned with the study of microorganisms in the soil, water and air and their application in bioremediation to reduce environmental pollution through the biological degradation of pollutants into nontoxic or less toxic substances. Field of environmental microbiology also covers the topics such as microbially induced biocorrosion, biodeterioration of constructing materials and microbiological quality of outdoor and indoor air. Keywords: microorganisms, environment, indicator microorganisms, biodegradation, bioremediation Gentlemen, it is the microbes who will have the last word. (Louis Pasteur)

4.1 Evolution of microorganisms Earth is about 4.5 billion years old and scientists estimate that life first emerged at least 3.8 billion years ago after the surface of crust had cooled enough to allow liquid water to form. Early Earth was inhospitable from time to time because space rocks crushed into the Earth’s surface. Some impacts were powerful enough to vaporize oceans and create clouds of steam which sterilized the Earth’s surface. Nonetheless, some microorganisms were able to survive this period deep underground while some may have had the capacity of modern microorganism to produce survival forms called endospores. Early in the planet’s history conditions were harsh. The Earth’s surface was exposed to strong ultraviolet (UV) radiation because the ozone layer was not yet formed in the atmosphere. Nevertheless, the prokaryotic microorganisms began to

This article has previously been published in the journal Physical Sciences Reviews. Please cite as: Briški, F., Vuković Domanovac, M. Environmental Microbiology. Physical Sciences Reviews [Online] 2017, 2 (11). DOI: 10.1515/psr-2016-0118 https://doi.org/10.1515/9783110468038-004

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4 Environmental microbiology

develop. The first prokaryotic microorganisms lived in anaerobic environment because atmosphere was a mixture of CO2, N2, and H2O vapour and in traces H2. O2 gas began to appear in significant amount in the Earth’s atmosphere between 2.5 and 2 billion years ago as a result of microbial metabolic process called oxygenic photosynthesis. Oxygenic photosynthesis which started around 3 billion years ago differed from earlier forms of photosynthesis and the bacteria responsible for this type of photosynthesis are called cyanobacteria. Cyanobacteria brought the O2 level of the Earth’s atmosphere up to 10 % of today’s level and due to it the formation of ozone layer started. O2 level was high enough to enable evolution of oxygen-utilizing organisms [1, 2]. An approximate timeline of the development of life on Earth is presented in Figure 4.1. Since many eukaryotes are O2 dependent, researchers had theorized that protists first appeared around 2 billion years ago but according to recent evidence the first protists appeared about 3 billion years ago. Although bacteria and archaea are older than protists, an early appearance of the first eukaryotes is evidenced with a high degree of diversity in this group. Algae appeared after cyanobacteria within the last 2 billion years, because their chloroplasts were derived from cyanobacteria. Fungi appeared during the last several hundred million years.

Appearance of eukaryotic microorganisms Appearance of first prokaryotes

Appearance of plants and animals Cyanobacteria introduce significant O2 into atmosphere

Earth’s crust cools

4

3

2

1

0

Billion years from present Figure 4.1: Approximate timeline in the history of life on Earth [1].

4.2 The microbial world: classification, metabolism and growth Microorganisms are the foundation for all life on Earth. They vary in their appearance, ability to carry out different biochemical transformations, ability to grow in wide variety of environments and in their interactions with other organisms. Due to a great variety of different organisms on Earth, a systematic approach to classifying these organisms is necessary. The science of classifying organisms is called taxonomy and the groups making up the classification hierarchy are called taxa. Nomenclature refers to the actual naming of organisms. The binominal system of nomenclature is

4.2 The microbial world: classification, metabolism and growth

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used for microorganisms. The names are given in Latin or are Latinized. The first word in the name is the genus, with the first letter always capitalized; the second is the species name, which is not capitalized. Both words are always italicized. Classification of well-known bacterium Escherichia coli is presented in Example 4.1. Example 4.1. Classification of bacterium Escherichia coli E. coli is a member of genus Escherichia. It was named after the person who first isolated and described it, Theodor Escherich. The species name comes from the location where it was found, in this case in human intestinal tract. Its classification is as follows: Domain: Bacteria, Phylum: Proteobacteria, Class: Gammaproteobacteria, Order: Enterobacteriales, Family: Enterobacteriaceae, Genus: Escherichia, Species: E. coli.

Traditional classification of living organisms was based on morphological differences like shape, colouring or appendages (flagella) extending from the cells. In the 1970s, a research by Woese and others suggested that life on Earth evolved along three evolutionary lineages. Analysis of 16S rRNA (ribosomal ribonucleic acid) has led to the modern phylogenetic classification of living organisms in three domains: Archaea, Bacteria and Eukarya. Phylogenetic information along with other taxonomic information has been used to construct the phylogenetic tree (Figure 4.2).

Bacteria

Archaea

Eukarya

Animals

Fungi Plants

Lower eukaryotes The first cell Figure 4.2: Schematics of universal phylogenetic tree evolved from a common ancestor.

Using the rRNA gene sequences of many different organisms resulted in formation of a tree with longer and shorter branches; the longer the branches lengths, the greater the diversity in the group. The branches lengths are shorter for newly evolved organisms such as fungi, plants and animals in comparison with the branches lengths for prokaryotic and lower eukaryotic microorganisms [1, 3]. Members of microbial world consist of two major cell types: the simple prokaryotic and the complex eukaryotic cells. Microscopically, the cells in domains Bacteria and

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Archaea look similar. They do not contain a membrane-bound nucleus or other intracellular lipid-bound organelles. Their genetic information is stored in a circular strand of deoxyribonucleic acid (DNA) in the nucleotide and cytoplasm is surrounded by a rigid cell wall. Due to structural similarities bacteria and archaea are prokaryotes but they differ in their chemical composition and therefore they are in different domains. The domain Eukarya is comprised of four kingdoms: Animalia, Fungi, Plantae and Protista. All members in this domain contain eukaryotic cells and this microbial world is composed of single-celled and multicellular organisms. The cells contain a membrane-bound nucleus and other internal organelles (mitochondria, chloroplast and cytoskeleton) that make eukaryotes more complex than the simple prokaryotes. Term microorganism is used to describe an organism that is so small that it cannot be seen without the use of microscope. Microscopy plays an integral role in the study of microorganisms and can provide extremely useful information about them. Even today, one of the most important tools for studying microorganisms is the brightfield light microscope that can magnify images 1000×. Most living microorganisms are nearly transparent and move rapidly about the slide. Consequently, cells must be immobilised and stained with dyes. Simple staining employs one dye to stain the cells. Differential staining is used to distinguish one group of bacteria from another. One of most frequently used staining procedures is the Gram stain (Example 4.2). Example 4.2. Gram staining is the procedure (Figure 4.3) by which bacteria can be separated in two major groups: Gram positive and Gram negative. Difference in the staining properties of these two groups is due to the difference in the chemical structure of their cell walls. This procedure was developed over a century ago by Dr. Hans Christian Gram.

PROCEDURE

Thin film of specimen spread over slide

Drying at room temperature

Flooding with stain Passing slide through flame

Steps in Gram staining 1. Crystal violet (primary stain)

Cells stain purple

2. Solution of iodine

Cells remain purple

3. Ethanol (decolourizer)

Gram-positive cells remain purple; Gram-negative cells become colourless

Figure 4.3: Staining bacteria for microscopic observation.

4.safranin (counterstain)

Gram-positive (G+) cells remain purple; Gram-negative (G-) cells appear red

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The bacteria are the smallest prokaryotic cells and the least structurally complex unicellular microorganisms. They possess the greatest metabolic flexibility. Typical shapes of common bacteria are: (a) sphere (coccus), (b) rod (bacillus) and (c) spiral (spirillum). Diameter of a typical cell is 1 µm. A representative of rod-shaped bacteria is presented in Figure 4.4(a). The cell wall contains chemical compound peptidoglycan, which is not found in organisms in other domains. They multiply by binary fission in which one cell divides in two cells, and many can move using flagella. The archaea are a group of ancient organisms and subdivisions include methanogens (methane producing), halobacteria (live in high-salt environments) and thermoacidophiles (grow best under high temperature and high acidity). The cells of archaea are somewhat similar to bacteria in size and shape; however, they are genetically and biochemically quite different and may be the oldest form of life on Earth. They also multiply by binary fission and move by means of flagella, but archaea do not have peptidoglycan in their cell walls. Members in the domain Eukarya consist of eukaryotic cells and diameter of a typical cell is 10–100 µm. Many fungi are microscopic, while others, like mushrooms, are macroscopic. All fungi have chitin in their cell walls. Yeasts are singlecelled fungi. Yeasts can be spherical, oval or cylindrical, and are usually 3–5 µm in diameter (Figure 4.4(b)). Yeasts can reproduce by asexual or sexual means.

(a)

(b)

Budding cells

(c)

Chain of spores

Hyphae

(d)

(e)

(f)

Rotifera Figure 4.4: Bright-field photomicrograph of cells: (a) rod-shaped bacterium Bacillus sp., (1000×), (b) yeast Saccharomyces sp., (400×), (c) mould Penicillium sp., (400×), (d) green algae Chlorella, (400×), (e) single-celled attached protist (stalked ciliates), (400×) and (f) multicellular Rotifera (100×).

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Asexual reproduction is by budding or fission. Moulds are filamentous fungi and have a mycelial structure. Long thin filaments on the mycelium are called hyphae. Some branches of mycelium may grow in the air and asexual spores (conidia) are formed on these aerial branches. Fungal spores are typically a single cell of about 3–30 µm in diameter, depending on the species (Figure 4.4(c)). Protozoa, slime moulds and unicellular algae as a single-celled organisms belong to the taxonomic kingdom of Protista. The algae are a diverse group of photosynthetic protists. Some of them are single-celled while others are multicellular, and they come in a great range of shapes and sizes, from spherical cells with 0.5 μm diameter (Prochlorococcus) to 60 m long multicellular thalli (Macrocystis). They all contain green pigment chlorophyll, but some of them also contain other pigments (Figure 4.4(d)). They reproduce asexually or sexually. The role of pigment is to absorb sunlight, which algae use as a source of energy. The cell walls of algae are rigid and are composed of cellulose. Diatoms are algae that have silicon dioxide incorporated into their cell walls. Some multicellular species contain other compounds such as carrageenan and agar in their cell walls. Protozoa are diverse groups of microscopic single-cell organisms and they are much larger (5–500 µm) than prokaryotes (Figure 4.4(e)). Protozoa are classified into three groups based on shape: ciliates, flagellates and amoebae. They do not have a rigid cell wall and many of them have a specific shape due to cytoskeleton just beneath the outer membrane of the cell. Metazoa – invertebrates are microscopic multicellular organisms (0.1–0.5 mm long) divided in several subgroups and among them are rotifers (Rotifera, Figure 4.4(f)). The body of a rotifer is divided into a head, trunk and foot, and is typically somewhat cylindrical. The organisms discussed above are all living members of the microbial world. Viruses are not living organisms and they consist of a piece of nucleic acid surrounded by protective protein coat. Viruses can only multiply inside living cells and therefore they are considered obligate intracellular parasites [1–4]. Environmental factors that influence microbial growth are temperature, oxygen requirements and pH and water availability. The right temperature, pH and moisture levels vary from one organism to another. Some of them can grow at ‒20 ° C in a brine to prevent freezing, while others can grow at 120 °C where water is under high pressure to prevent boiling. Microorganisms that grow optimally below 20 °C are called psychrophiles, those with temperatures optima in the range of 20 ° C to 50 °C are mesophiles, while those that grow best at temperatures higher than 50 °C are thermophiles. Hyperthermophiles have an optimum growth temperature between 70 °C and 110 °C and these are usually members of the Archaea. Cells that require O2 for growth and metabolism are obligate aerobes; obligate anaerobes cannot multiply in the presence of O2, while facultative anaerobes grow best if O2 is present, but can also grow without it. Microaerophiles require small amounts of O2 and aerotolerant anaerobes (obligate fermenter) are indifferent to O2. Each bacterial species can survive within a range of pH values, but within this

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range it has a pH optimum. Neutrophiles multiply in the range of pH 5 to 8, acidophiles grow optimally at a pH below 5.5 and alkalophiles above 8.5. Finally, all microorganisms require water for growth. Growth of any microorganisms depends not only on a suitable physical environment, but also on available source of chemicals to use as nutrients. All cells contain the macromolecules as follows: carbohydrates, lipids, proteins, nucleotides. Nucleotides as monomers are needed for DNA and RNA synthesis and they play important role in cellular energetics. Elements that make up cell constituents are called macronutrients or major elements (C, O, H, N, S, P, K, and Mg). Trace elements are also essential to microbial nutrition. The most widely needed trace elements are Fe, Zn and Mn. The elements needed under specific growth condition are Cu, Co, Mo, Ca, Na, Cl, Ni and Se. Some bacteria, especially methanogens, need Na for ion balance. Element Na is important in the transport of charged species in eukaryotic cells. Some halobacteria and marine microorganisms need Cl‒. Microorganisms derive energy either from sunlight or by metabolising chemical compounds. Prokaryotes can live in many environmental habitats because they are able to use diverse sources of energy and carbon. Photoautotrophs use the energy of sunlight and CO2 in the atmosphere to synthesize organic compounds required by many other organisms. Cyanobacteria are important photoautotrophs that inhabit fresh and saltwater habitats. Chemoautotrophs or chemolithotrophs use inorganic compounds (H2, NH3, NO2‒, Fe2+, and H2S) for energy and derive their carbon from CO2. Photoheterotrophs use the energy of sunlight and derive their carbon from organic compounds. Chemoheterotrophs or chemoorganotrophs use organic compounds for energy and as a carbon source. Cells synthesize only the enzymes they require for growth. Under the changed environmental conditions, additional or different enzymes may be important. Enzymes are proteins that act as biological catalysts, facilitating the conversion of substrate into product. They usually act on only one, or a very limited number of substrates. More than a 2000 different enzymes are known. They are named by adding the suffix –ase to the end of the substrate name, like amylase, or reaction catalysed, such as alcohol dehydrogenase. Some enzymes have a simple structure, while others have more than one subunit. Some protein enzymes require a nonprotein group for their activity, such as cofactor (metal ions Mg, Zn, Cu), or coenzyme that are non-protein organic compounds (e.g. nicotinamide adenine dinucleotide – NAD+), or some vitamins. Differences in microbial metabolisms can be attributed partly to genetic differences and partly to differences in their responses to changes in their environment. Even the same species may produce different products when grown under different nutritional and environmental conditions. Living cells require energy for biosynthesis, transport of nutrients, motility and maintenance. Two primary functions of cellular metabolism are catabolism and anabolism. Catabolism is the degradation of a substrate to more highly oxidized end products for the purpose of generating

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energy and reducing power. Anabolism is the biosynthesis of complex compounds from simpler compounds, usually with the consumption of energy and reducing power. Energy in biological systems is stored and transferred via adenosine triphosphate (ATP), which contains high energy phosphate bonds. Chemoheterotrophs use two processes to provide energy to form ATP: substrate-level phosphorylation and oxidative phosphorylation. Photosynthetic organisms can generate ATP using the process of photophosphorylation, utilizing radiant energy of the sun. There are other compounds analogue to ATP, which store and transfer high-energy phosphate bonds, but not to the extent of ATP. Glucose is a major carbon and energy source for many heterotrophic organisms. Several different metabolic pathways are used by different organisms for catabolism of glucose. Three of the most important metabolic pathways are: a. Embden-Meyerhof-Parnas (EMP) pathway or glycolysis – converts glucose to pyruvate and produces initial amount of ATP. b. Krebs, tricarboxylic acid cycle (TCA), or citric acid cycle – oxidizes pyruvate through acetyl-CoA into CO2 and H2O, and produces a large amount of ATP. c. The pentose-phosphate or hexose-monophosphate (HMP) pathway – converts glucose-6-phosphate into variety of carbon skeletons (C3, C4, C5), with glyceraldehyde-3-phosphate as the end product. Although all three pathways can have catabolic and anabolic roles, the EMP and TCA cycles are the primary means for energy generation, while HMP plays a key role in supplying carbon skeletons and reducing powers for use in biosynthesis. In prokaryotes a single glucose molecule will yield up to 24 mol of ATP, while in eukaryotes up to 36 mol of ATP. Reducing power is stored in coenzyme nicotinamide adenine dinucleotide NADH (oxidized form is NAD+) and nicotinamide adenine dinucleotide phosphate NADPH (oxidized form is NADP+). Reducing power can be used to generate ATP through electron transport chain. When O2 is the final electron acceptor for this reducing power, the process is called aerobic respiration. If another electron acceptor such as NO3‒ or SO42‒ is used in conjunction with electron transport chain, then the process is called anaerobic respiration. Anaerobic respiration is a less efficient form of energy transformation than aerobic respiration. Cells that obtain energy without using the electron transport chain use fermentation. Substrate-level phosphorylation supplies ATP. The end products of fermentative metabolism such as ethanol or lactic acid are formed in response to the cells’ need to balance consumption and the production of reducing power. Autotrophic organisms use CO2 as their carbon source to incorporate carbon from CO2 into cellular material. Energy is obtained either through sunlight (photoautotroph) or oxidation of reduced inorganic chemicals such as H2S, NH3 or Fe2+ (chemoautotroph). By knowing environmental and nutritional factors that influence growth of specific prokaryotes, it is possible to provide appropriate conditions for their cultivation in laboratory. These include a medium on which to grow the organism and a

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suitable atmosphere. For routine purposes many types of complex media are used. Commonly used complex medium, nutrient broth, consists of only peptone (protein hydrolysed to amino acids and short peptides), beef extract and water. Nutrient agar results if agar (polysaccharide from algae) is added to nutrient broth. Chemically defined media are composed of mixtures of pure chemicals. An example is glucosesalts medium, which supports the growth of bacterium E. coli, and contains ingredients as follows: glucose, K2HPO4, KH2PO4, MgSO4, (NH4)2SO4, CaCl2, FeSO4 and water. Selective and differential media are used for the purpose of detecting or isolating an organism that is a part of a mixed bacterial population. Selective medium types are formulated to support the growth of one group of organisms such as Gramnegative bacteria, but inhibit the growth of other like Gram-positive bacteria. Differential media are widely used for differentiating closely related organisms or groups of organisms. Some media may possess both, selective and differential properties, allowing them to grow certain groups of organisms of interest and give the investigator a way to discern differences in the group based on a visible reaction with the media. These media can be powerful diagnostic tools in environmental settings. Furthermore, an appropriate atmospheric condition for microbial growth has to be obtained. Obligate aerobes grow best when tubes or flasks containing media are shaken, providing maximum aeration. Some other microbial species requires atmospheric condition with increased CO2, microaerophilic or anaerobic conditions. The most widely used methods [1–3, 5] in the study of microorganisms present in different samples is their growth in a liquid medium, followed by dilution of the sample and plating on a solid agar medium. The theory is that one colony arises on a solid agar medium from one microbial cell. Each colony is then referred to as a colony forming unit (CFU) and the result of the analysis expressed in terms of CFU/mL or CFU/g of sample. Except for providing an estimate of bacterial numbers, this procedure allows obtaining pure culture isolates. Bacterial growth can be measured by direct cell counts and viable cell counts. Direct microscopic count is one of the most rapid methods of determining the number of cells in a suspension, but generally does not distinguish living and dead cells. Viable cell counts are used to quantify the number of cells capable of multiplying. Plate counts and membrane filtration both measure the concentration of cells by determining the number of colonies that arise from a sample added to an agar plate. The two different plating methods pour plate and spread plate, differ in how the suspension of microorganisms is applied to the agar plate. A simple count of the colonies determines how many cells were in the initial sample. The ideal number of colonies to count is between 30 and 300. However, samples frequently contain many more microbial cells than this number and therefore it is necessary to dilute the samples before plating out the cells. The sample is diluted in 10-fold increments and a sterile physiological saline (0.9 % NaCl in water) is used to make the dilutions (1 mL sample in 9 mL saline solution). In the pour plate method, 1.0 mL of the final dilution is transferred into sterile Petri dish and then overlaid with melted nutrient

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agar that has been cooled to 45 °C. At this temperature, agar is still liquid. Petri dish is then gently swirled to mix microbial cells with liquid agar. When the agar hardens the individual cells are fixed in place and, after incubation, distinguishable colonies appear on the agar surface (Figure 4.5).

Add 1 mL of culture

Transfer 1 mL

10 mL

1/10 (10-1)

Transfer 1 mL

1/100 (10-2)

Transfer 1 mL

1/1000 (10-3)

1/10000 (10-4)

Add 1 mL in plate

Confluent growth Too many to count

42 colonies

Too few to be statistically valid

Number of colonies × dilution factor = cells (CFU)/mL of original culture 42 × 103 × 1 (1 mL plated out) = 4.2 × 104 CFU/mL Figure 4.5: Pour plate method – serial dilutions for the estimation of viable cell count.

In the spread plate method 0.1 mL of the final dilution is transferred directly onto the plate already containing a solidified nutrient agar medium. This solution is then spread over the surface of agar with previously sterilized bent glass rod. Membrane filtration is used when the numbers of organisms in a sample are relatively low, as might occur in dilute environment such as natural waters. This method concentrates the bacteria by filtration before they are plated. A known amount of liquid is passed through a sterile membrane filter (pore sizes 0.2–0.45 µm), the filter is placed on an appropriate agar medium and then incubated. The number of colonies that grow on the filter indicates the number of microbial cells that were in the volume filtered and the result is reported per 100 mL of original sample. The most probable number (MPN) method is a statistical assay of cell numbers based on the theory of probability. To determine the MPN, three sets of three or five tubes containing the same growth medium are prepared. Each set receives a measured amount of sample such as water or soil. What is important is that the second set receives 10-fold less than the first and the third set 100-fold less. After incubation, the presence (e.g. gas production or precipitate) or absence of growth in each set is noted. The results are then compared against an MPN table, which gives a statistical estimate of the cell concentration, and expressed as MPN/100 mL of original sample. Instead of measuring the number of cells the cell mass can be determined.

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This can be done by measuring the turbidity or dry weight. A spectrophotometer is used to measure cloudiness or turbidity of a bacterial suspension as a broth culture. To measure the wet weight, cells growing liquid mediums are centrifuged down, liquid removed and cell mass weighted. The dry weight of the cell mass is determined by drying the centrifuged cells at 105 °C for several hours before weighing them. In the laboratory, bacteria are typically grown in broth contained in a tube or flask. When grown under batch conditions a population of bacteria goes through four distinct stages: in lag phase cells synthesize macromolecules prior to active multiplication; in exponential or log phase, cells divide at a constant rate and their numbers increase by the same percentage during each time interval (generation time is measured during this active multiplication); cells enter the stationary phase when they have exhausted their supply of energy and nutrients and the total number of viable cells in the population remains relatively constant; death phase is the period when total number of viable cells in the population decreases as cells die off at a constant rate. Theoretically, the time taken for cell division to occur is the mean generation time or doubling time. This varies depending on the species of microorganisms and conditions in which it is grown. For example, one of the most intensively studied prokaryotic and eukaryotic model single-celled organisms bacterium E. coli can double in 20 minutes under the laboratory conditions and yeast Saccharomyces cerevisiae in 90 to 120 minutes. Most bacteria reproduce by binary fission, which results in doubling of the number of viable bacterial cells. The relationship of cell numbers and generations can be expressed in a series of equations. Starting with an initial population N0, the total population N at the end of a given time period would be expressed as eq. (4.1): N = N0
2n

(4:1)

where 2n is the bacterial population after n generations. Solving the equation for n, eq. (4.2): log N = log N0
n log 2 ! n =

log N − log N0 log 2

(4:2)

The number of generations can be calculated if the initial population N0 and the population N after time t are known. The generation time tg is equal to t (the time which elapsed between N0 and N) divided by the number of generations n, eq. (4.3): tg =

t t
log 2 ! tg = N n log No

(4:3)

Calculation of mean generation time of bacterial population is presented in Example 4.3.

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Example 4.3. What is a generation time of bacterial population that increases from 1 × 104 cells per 1 mL to 1 × 107 cells per 1 mL in four hours of growth?

tg =

t
log 2 240
log 2 240
0.301 ! tg = ! tg = N 3 107 104

Answer: tg = 24 minutes

The selection of methods used for microbial identification depends on the type and nature of the microorganism. The methods commonly used in identification and substantiation of taxonomic classification of microorganisms are phenotypic analysis and molecular methods. Phenotypic analysis often involves growth of microorganisms as pure culture on an artificial media, followed by visual observation of colony morphology such as shape, size, surface characteristics and pigmentation and cell morphology (cell wall characteristics – Gram-staining, sporulation characteristics, mechanisms of motility and other cellular inclusions) using microscopy. For biochemical test specific growth media, nutrients, chemicals or growth conditions are used. These tests include: utilization of carbon and nitrogen sources, growth requirements (anaerobic or aerobic; temperature-optimum and range, pH optimum and range), generation of fermentation products, production of extracellular enzymes (e.g. amylase, protease and cellulase, which hydrolyses starch, protein and cellulose, respectively; Figure 4.6) or other compounds.

(a)

(b)

(c)

Figure 4.6: Amylolytic activity (a) and proteolytic activity (b) indicated by haloes around a colonies of mould Aspergillus niger and filamentous bacterium Streptomyces sp. and (c) cellulolytic activity indicated by growth of mould Trichoderma viride on wood chip as a sole source of carbon.

Identification, using molecular methods, relies on the comparison of the nucleic acid sequences (DNA, RNA) or protein profiles of a microorganism with documented data on known organisms. The molecular methods are considered sensitive enough to allow detection of low concentrations of viable or non-viable microorganisms in both pure cultures and complex samples (e.g. soil, water and other samples). One of the

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methods is polymerase chain reaction (PCR), which consists of sequence comparisons of conserved genomic regions such as 16S or 18S rRNA. Reliable genotypic identification requires databases with accurate and complete sequence information from a large number of taxa. Commonly used gene sequence database is GenBank provided by the National Centre for Biotechnology Information (NCBI, http://www. ncbi.nih.gov). Microbial identification of bacterium Pseudomonas aeruginosa is described in Example 4.4. Example 4.4. A nicotine degrading bacterium was isolated from the composting mass [6]. To identify isolated culture phenotypic and molecular method were conducted. According to phenotypic analysis colonies of isolated pure culture were circular, raised and produced water soluble yellow-green pigment. Bacterial cells observed with a bright field microscope were rod-shaped and motile, and after Gram staining cell were Gram negative. A series of biochemical tests were carried out applying API 20 NE test. The biochemical reactions were read according to the Reading Table and by referring to the Analytical Profile Index, the bacterial culture was identified as Pseudomonas aeruginosa. Although it is known that the maximum temperature for growth of P. aeruginosa is 42 °C, this isolated species was quite actively degrading nicotine at 50 °C during composting tobacco waste. The molecular characterisation that uses 16S rRNA gene sequence to identify bacterium, confirmed that isolated species is P. aeruginosa FN (FN-fast nicotine degrading).

4.3 Microbial diversity in the environment Microorganisms inhabit terrestrial and aquatic ecosystems, including geographical locations considered to be extreme to life [2, 5, 7]. Among their many roles, they are necessary for cycling of carbon, nitrogen, phosphorus and sulphur (biogeochemical cycles), all essential components of living organisms. Since the Earth is a closed system, in order for life to continue, dead organisms must be degraded to their component parts to provide the ingredients needed to grow new living organisms. Microorganisms are recyclers of biomass on Earth and without their recycling activities life on Earth would quickly come to a halt. Microorganisms are also food for some higher organisms and they are at the base of all the Earth’s food chains. Apart from recycling dead biological material, some microorganisms also utilize metals and thus recycle non-biological materials. The biodeterioration of man-made compounds by some microorganisms can be a problem (e.g. in the case of paints and plastics). Some fungi attack and degrade man-made materials such as paper, leather, jet fuel, etc. Terrestrial environments are the richest and the most complex and vary from a rain forest to a desert, but all soils contain a rich diversity of microorganisms. Soil is three-phase system consisting of: (a) a solid or mineral inorganic phase that is often associated with organic matter; (b) a liquid or solution phase that contains almost all essential minerals (e.g. NO3‒, Cl‒, CO32‒, SO42‒, Ca2+, Mg2+, Na+, K+), which are primary source of inorganic nutrients for plant roots and (c) a gas phase or atmosphere. The density and composition of microbial species of the soil is affected by environmental

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conditions. For example, wet soils are unfavourable for aerobic microorganisms because the free air spaces are filled up with water. When the water content of soil drops to a very low level (drought or desert) the metabolic activity and number of soil microorganisms decrease. Acidity, temperature and nutrient supply also have influence on microbial activity and diversity. Humification – humus as regulator of soil structure, source of plant nutrients, carbon pool and carbon – CO2 sequestration. Representative sampling of soils is crucial for determination of microbial diversity, interactions between them and shifts in microbial population in soil. Soil samples are obtained with a shovel or a soil auger. Sampling strategy requires taking into consideration the objective of the study, a level of precision of the data needed and sampling requirements (sampling sites, numbers and types of samples, size of sample units, etc.). Methods of soil sampling can be random, transect, two-stage or systematic grid [5, 7, 8]. The traditional methods of microbiological analysis of soil samples include cultural assays utilizing dilution and plating methodology (Figure 4.7 and Figure 4.8) or direct count

(a)

(b)

(c)

Figure 4.7: Bacterial colonies that result from incubation following dilution and plating of soil sample. The plate on the left (a) has the most bacterial colonies (lowest soil dilution). The other two plates (b and c) result from subsequent dilutions. From these three plates, plate B should be counted since it has between 30 and 300 colonies.

(a)

(b)

(c)

Figure 4.8: Fungal colonies that result from incubation following dilution and plating of soil sample. The plate on the left (a) has the most fungal colonies (lowest soil dilution). The other two plates (b and c) result from subsequent dilutions. From these three plates, plate C should be counted since it has between 30 and 300 colonies.

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assays. The number of bacteria in sample is expressed in terms of CFU/g soil (dry weight). As moist soil is originally weighed out, therefore actual dry weight of soil depends on soil moisture at the time of diluting. Molecular methods such as DNA or RNA sequencing are applied for identification of nonculturable microorganisms. Surface soils are occupied by indigenous populations of archaea, bacteria, fungi, algae, and protozoa, and the microbial distribution depends on soil texture and structure. The microbial communities within the subsurface are lower in number and less diverse than in surface soils. Since nutrients are much more limited in the subsurface, a greater proportion of the population may be in a nonculturable state. In deep saturated zones, the numbers are even lower with limited microbial diversity and include a range of aerobic and facultative anaerobic chemoheterotrophs such as denitrifiers, methanogens, sulphate-reducers, sulphur-oxidizers, nitrifiers, and nitrogen-fixing bacteria. Prokaryotes are the most numerous soil inhabitants. Gram-positive (G+) bacteria are more abundant in soils than Gram-negative (G-) bacteria. Among the most common are G (+) spore-forming, rod-shaped bacteria of genera Bacillus and Clostridium. These species form endospores inside vegetative cells, enabling them to survive adverse periods such as drought or extreme heat. Filamentous G (+) bacteria of the genus Streptomyces produce desiccation-resistant spores unrelated to endospores. They also produce metabolites called geosmin, which give soil its characteristic musty odour. Some G (-) chemoheterotrophic bacteria adapted to live in terrestrial environments are species of Azotobacter, Agrobacterium, Rhizobium and Pseudomonas, and among chemoautotrophs nitrifying bacteria such as species of Nitrosomonas (transform ammonium to nitrite) and Nitrobacter (oxidize nitrite to nitrate). Importance and practical use of nitrogen-fixing bacteria is for bacterisation of legume seeds (symbiotic – Rhisobium sp. and non-symbiotic Azotobacter chroococum). Prokaryotes are most numerous in soil, but biomass of fungi (eukaryotes) is much greater. Most fungi are aerobes and they are usually found in the top 10 cm of soil. Fungi derive energy from organic material and they are found wherever organic materials are present. The soil fungi are crucial in decomposing plant matter, degrading and using complex macromolecules such as lignin and cellulose. Many soil bacteria and fungi are important in nutrient cycling and removal of organic contaminants by the processes of biodegradation and bioremediation. Various protists are also found in most soils. Algae generally depend on sunlight for energy and most protozoans require O2, so they are found near the soil surface [9]. Aquatic environments occupy more than 70 % of the Earth’s surface and main types are: surface waters (springs, streams, rivers and lakes), marine environments (seas, oceans) and ground waters. There are many types of springs (cold, thermal, hot and specialized – iron, sulphur, radioactive). Cold springs are habitat for bacteria and algae, thermal or hot springs for many different species of archaea and thermophilic bacteria, iron springs for bacterial species Gallionella and Sphaerotilus and sulphur springs for photosynthetic and non-photosynthetic sulphur bacteria. Water from a

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source like a spring, rain or snow melt begins to flow down, and small streams are formed. These streams may slowly join together to form a larger stream or river. Streams and rivers accumulate organic matter and heterotrophic population from surrounding terrestrial environment thus a profile of microorganisms in streams and rivers resembles terrestrial. The types and relative numbers of microorganisms inhabiting lakes and marine environments depend on concentration of dissolved O2 and nutrients, temperature and sunlight. The upper layer is oxygen-rich due to the activities of many photosynthetic organisms such as cyanobacteria. In contrast, the bottom layer of lakes may be anaerobic due to the consumption of O2 by heterotrophs. In deep sea, water is O2-saturated due to mixing associated with tides, currents, and wind action. Ground waters are found inland in the subsurface zone and include shallow or deep aquifers. Microorganisms are the sole inhabitants and bacteria are predominant. In general, here microbial activity is low due to the poor concentration of nutrients. Ground water, rivers and lakes are important sources of fresh water. Man-made aquatic environment comprises of stagnant ponds, swimming pools, drainage ditches and wastewaters treatment plants in industrial and urbanized regions [9]. Water and wastewater sampling is generally performed by one of two methods; grab sampling or composite sampling. Grab samples are single samples collected from a specific spot at a site over a short period of time (typically seconds or minutes) for: protected groundwater supplies, water supplies receiving conventional treatment, some well-mixed surface waters, wastewater streams, rivers, large lakes, shorelines or estuaries. Composite samples can be obtained by combining portions of multiple grab samples or by using specially designed automatic sampling devices. Membrane filtration (Figure 4.9(a)) and multiple-tube MPN method (Figure 4.10(a))

(a)

(b) (2)

(3)

(4)

Figure 4.9: (a) Membrane filtration apparatus: 1. water sample, filtration funnel, 3. vacuum pump, 4. selective agar media; and (b) appearance of blue colonies of faecal coliform bacteria on membrane filter after incubation on mFC agar for 24 hours at 44.5 °C

4.3 Microbial diversity in the environment

(a)

101

(b)

(c)

Figure 4.10: MPN dilution series: (a) test tubes after incubation - three series with five replicate tubes, (b) positive test tube in comparison with negative one and (c) dark colour colonies of iron bacteria with metallic shine on Winogradsky agar.

are applied for microbiological analysis of natural waters and wastewater streams; however more polluted water will likely require a greater dilution range [10]. Total and faecal coliform bacteria (TC and FC) have been used to evaluate the general quality of water. Faecal coliform bacteria and their representative E. coli originate specifically from the intestinal tract of warm-blooded species (e.g. humans, beavers, racoons, etc.) and are cultured by increasing the incubation temperature to 44.5 C and using selective growth medium such as mFC broth or mFC agar (Figure 4.9(b)). Two other groups of bacteria that are present in faeces are: faecal streptococci (FS) and Clostridium. Clostridia spores can survive a long time during adverse conditions. These genera occur naturally in soils and polluted waters, but also indicate a faecal contamination by warm-blooded animals. The ratio of faecal coliforms to faecal streptococci (FC:FS) can provide information on the source of contamination. Human faeces have much more FC than FS, while FS are more common in animal faeces. Comparing the numbers of FC to FS is handy for getting an idea as to whether the water has been polluted with human faecal wastes (>4:1 ratio) or animal wastes (98 % for particles >0.5 µm) and are simple to install and maintain. However, they require large pressure drops leading to higher power requirements than other scrubber designs. Other often used designs involve packed scrubbers and mechanically aided scrubber. Packed scrubbers are occasionally used for particulate control, but they are restricted to separation of fine and/or soluble particulates, aerosol and mists, because of possible blockage of nozzles and

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plugging of bed. In line with this, they are limited to applications with low particle content (1300 °C) due to complex reaction of oxygen and nitrogen with high energetic free radicals (O, N, OH, H and hydrocarbons that have lost one or more hydrogen). The catalysts are usually based of combination of a noble and other metals (Pd, Pt, Cr, Mn, Cu, Co, and Ni) deposited on an alumina monolithic support to minimize the pressure drop, which is one of the critical parameters of the incinerator designs. Limitation of the catalytic systems is catalyst deactivation, due to the presence of contaminants, attrition or catalyst sintering. Catalytic systems are suited for a gas stream with low VOC content. Depending on the types of heat recovery, both thermal and catalytic incinerators can be classified into two categories: recuperative and regenerative. The recuperative incinerator can recover about 70 % of the waste heat from the waste gases, while the regenerative incinerator can recover up to 95 % of the energy. Flare gas systems are used in a wide variety of applications and are generally used to burn off excess gas, usually hydrocarbons. A flare gas system may contain open flame flares or combustors (flame enclosed) with small differences between them. A flare can be used to control almost any emission stream containing VOCs [23, 28]

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7.3.4.5 Biological waste gas treatment In the biological control systems gaseous pollutants are converted into less harmful or harmless substances by microorganisms. Almost all kind of organic (hydrocarbons, chlorinated hydrocarbons, ketones, esters, aldehydes, odors) and inorganic pollutants (NH3, NOx, H2S, CS2) can be treated by microorganisms. There are two groups of microorganisms that may be used for this purpose: autotrophic bacteria which are particularly suitable for the conversion of inorganic substances and heterotrophic bacteria which are well suited for the conversion of organic pollutants. The microorganisms oxidize the pollutants and produce cell substrate, CO2, water and inorganic salts. This process takes place in the presence of water and it is possible only for the very low pollutant concentration. Biological systems are especially suitable for degradation of VOCs, odors and toxic compounds. Obviously, they are similar to biological systems used for treatment of the wastewater and can be divided into three categories: biofilters, biotrickling filters and bioscrubbers (Table 7.3). Table 7.3: Types of biological air pollution control systems [22]. Application

Biomass

Water phase

Biofilter Biotrickling filter Bioscrubber

fixed fixed flowing (suspended)

fixed flowing flowing

Biofilms of microorganisms are grown on porous media in biofilters and biotrickling filter, while a contaminated gas stream is passed through a porous packed bed at a low velocity. The main difference between those two systems is that liquid phase is stationary in a biofilter and moves through the porous media in a biotrickling system. Bioscrubbing combines wet gas scrubbing (absorption) and biodegradation. The scrubbing water with suspended microorganisms is recirculated through the reactor and the absorbed pollutants are degraded in aeration sludge tank. Bioscrubbing is suitable for removing of readily biodegradable compounds, such as NH3, amines, hydrocarbons, H2S and odorous pollutants. Biofiltration mainly use compost as the porous media is cheapest and thus widely used biological waste gas treatment for the removal of low concentration of pollutants that are easily soluble in water [10, 22]. Readers interested in the additional information on design and scale-up principles and operational guidance regarding to the control devices for cleaning gaseous pollutants can refer to available literature [5, 10, 13, 15, 23, 31].

References [1]

https://www.theatlantic.com/photo/2012/12/2012-the-year-in-volcanic-activity/100423/. Accessed: 15 May 2017.

References

[2]

[3]

[4] [5] [6] [7] [8] [9]

[10]

[11]

[12] [13] [14] [15] [16] [17] [18] [19] [20] [21] [22] [23] [24] [25]

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Trends in global CO2 emissions: 2016 Report. The Hague: PBL Netherlands Environmental Assessment Agency and European Commission, Joint Research Centre, 2016. Available at: http://www.pbl.nl/en/publications/trends-in-global-co2-emissions-2016-report. Accessed: 18 May 2017. Stocker TF, Qin D, Plattner GK, Alexander SK, Allen NL, Bindoff FM, et al. Technical summary, In: The physical science basis. Contribution of Working Group I to the Fifth Assessment Report of the Intergovernmental Panel on Climate Change, IPCC, 2013:33. Kremer M. Population growth and technological change: one million B. C. to 1990*. Q J Econ 1993;108:681–716. Cooper CD, Alley FC. Air pollution control: a design approach. Long Grove: Waveland Press, Inc., 2002. https://www.epa.gov/research/strategic-research-action-plans-2016-2019. Accessed: 24 May 2017. http://www.epa.gov/iaq/pubs/hpguide.html. Accessed: 18 May 2017. http://www.who.int/mediacentre/news/releases/2016/air-pollution-estimates/en/. Accessed: 20 July 2017. Air quality in Europe: 2016 report. Luxembourg: European Environment Agency, 2016. Available at: https://www.eea.europa.eu/publications/air-quality-in-europe-2016. Accessed: 20 May 2017. Best available techniques (BAT) reference document for common waste water and waste gas treatment/management systems in the chemical sector. Luxembourg: Publication office of the European Union, 2016. Available at: http://eippcb.jrc.ec.europa.eu/reference/BREF/ CWW_Bref_2016_published.pdf. Accessed: 18 May 2017 Petrović M, Tomašić V, Macan J. Environmental pollution. In: Macan MK, Petrović M, editors. Environmental analytics. Zagreb, Croatia: HINUS and Faculty of Chemical Engineering and Technology University of Zagreb, 2013:65. http://ec.europa.eu/environment/archives/air/stationary/solvents/index.html. Accessed: 21 May 2017. Schnelle KB, Brown CA. Air pollution control technology handbook. Boca Raton: CRC Press, 2002. http://schooltutoring.com/help/biology-review-of-the-ozone-hole-and-global-warming/. Accessed: 15 May 2017. De Nevers N. Air pollution control engineering. New York: McGraw Hill, 1995. https://chem.libretexts.org/Core/Physical_and_Theoretical_Chemistry/Kinetics/ Case_Sudies%3A_Kinetics/Depletion_of_the_Ozone_Layer. Accessed: 22 May 2017. Middlebrook AM, Tolbert MA. Stratospheric ozone depletion. Sausalito: University Science Books, 2000. http://infographics.pbl.nl/website/globalco2-2016/. Accessed: 18 May 2017. May 2017 http://eur-lex.europa.eu/legal-content/EN/TXT/PDF/? uri=CELEX:32010L0075&qid=1496146818076&from=en. Accessed: 23 May 2017. May 2017. Accessed: 20 May 2017 https://beeindia.gov.in/sites/default/files/2Ch8.pdf. Boubel RW, Fox DL, Turner DB, Stern AC. Fundamentals of air pollution control. San Diego: Academic Press, 1994. Cooper CD, Theodore L, Buonicore AJ. Industrial air pollution control equipment for particulates. Cleveland: CRC Press, 1976. Bauer H, Varma YB. Air pollution control equipment. Berlin: Springer Verlag, 1981. Wark K, Warmer CF. Air pollution – its origin and control. New York: Harper & Row, 1981. Kumar KS, Chenchaiah S. Controlling industrial air pollution emissions. In: Proceedings of International Conference on Impact of Industrialization on Environmental Pollution – Its Control and Abatement, Orissa, India, 2006:86–92.

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[26] Meikap BC, Swar AK, Mohanty C, Sahu JN, Hung YT. Air pollution and its control. In: Hung YT, Wang LK, Shammas NK, editors. Handbook of environment and waste management: air and water pollution control. Singapore: World Scientific Publishing Co., 2012. [27] Weiner RF, Matthews R. Environmental engineering. Amsterdam: Butterworth Heinemann, 2003. [28] Vallero DA. Air pollution. Kirk-Othmer encyclopedia of chemical technology. John Wiley & Sons, 2015. [29] Chandrappa R, Kulshrestha UC. Sustainable air pollution management- theory and practice. Switzerland: Springer Int. Pub., Environmental Science and Engineering, 2016. [30] Pham TD, Lee BK, Lee CH, Nguyen MV. Emission control technology. In: Nejadkoorki F, editor(s). Current air quality issues. Rijeka, Croatia: InTech, 2015. [31] Reynolds JP, Jeris JS, Theodore L. Handbook of chemical and environmental engineering calculations. New York: Wiley InterScience, 2002.

Questions and exercises to get you thinking – – – – – –

– – – – – – – –

What is the difference between primary and secondary air pollutants. Give some examples! Explain the greenhouse effect and specify some greenhouse gases! What is “sick building syndrome” and what does it link to? What are you doing to improve the air quality in your household? What are the major parameters that influence dispersion of air pollutants in the atmosphere? Describe typical sources and types of air emissions resulting from the oil refineries. What are examples of prevention pollution practice in this industry which kind of and which kind of the emission control equipment are used for the same purpose? Compare the major types of air pollution control devices used for particulates removal. Visit the Web and make a list of suppliers for these devices. Explain the better efficiency of multiple cyclones in comparison to a single cyclone. Describe the processes of absorption and desorption. Explain the similarities and differences of these processes. Adsorption isotherms can be described by different equations. List some of them! Describe the characteristic types of scrubbers that can be used for the simultaneous removal of particulates and gaseous pollutants. Does the Henry’s law absorption limit influence the amount of air pollutant that can be absorbed in a wet scrubbing type system? Compare the most important advantages and disadvantages of thermal and catalytic oxidizers! Explain some heat recovery options during the incineration process.

Danijela Ašperger, Davor Dolar, Krešimir Košutić, Hrvoje Kušić, Ana Lončarić Božić and Marija Vuković Domanovac

8 Water and wastewater treatment engineering Abstract: This chapter introduces water and wastewater characterization and gives an overview of the most important instrumental techniques used in water analysis. Pollution sources, origin of pollutants (inorganic, artificial organic), and modern removal techniques are particularly emphasized. The chapter describes the basic principles of biological water treatment, as well as modern processes involving membrane separation processes and advanced oxidation processes. Keywords: water, wastewater, characterization, membrane separation processes, biological treatment, advanced oxidation processes

8.1 Water and wastewater characterization and analysis Water is in fact the most widespread mineral substance on the earth’s surface. A casual observation of the world map would suggest that the supply of water is endless since it covers over two-third of the earth’s surface. However, we cannot use it directly since 90 % is in the salty oceans, 2 % is tied up in the polar ice caps, and most of the remainder is beneath the earth’s surface. Therefore only a small fraction of the water in the world is available to manage for human use. It is self-evidently an essential for life and many chemical analyses are carried out to ensure that water of appropriate quality is supplied for human consumption. Water has a wide variety of end users associated with it, like for recreation (swimming, boating and fishing), and drinking are common water usages for families, just as cooling, washing, and steam generation are common usages of water for industry. Each of these usages has different water quality criteria. Commonly there is some confusion between criteria and standards. Criteria are the scientific requirements which a water source must meet in order to support a designated use. Thus water quality criteria govern the input of water to a particular use and will be different for each intended use. Standards, on the other hand, govern the quality of the water after the user is through with the water and before he discharges it back to the environment [1, 2]. Water quality criteria depend upon the use of the water and vary considerably in the number and levels of the parameters to be considered. The water quality criteria for streams has resulted in the development of four primary classes of water, where it is probably the single most important criterion used in classifying a water as “polluted” is the microbial count: 1. Class A: Potable water supply – quality criteria: microbiological counts, color, turbidity, pH, dissolved oxygen, toxic materials, taste, odor, temperature; https://doi.org/10.1515/9783110468038-008

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Class B: Bathing, primary contact recreation, fishing – quality criteria: same as A, but less stringent levels; 3. Class C: Industrial, agricultural, fishing, navigation – quality criteria: dissolved oxygen, pH, suspended solid, temperature; 4. Class D: Cooling, sailing – quality criteria: floating material, pH, suspended solids [2].

2.

Quality criteria for wastewater uses are varied and generalizations are difficult. The bridge between the discharge of the water and the standard involves water treatment and purification. Since most industrial and domestic application use water for solids transport or for dissolving solids, it is imperative that many of these impurities be removed before the water is discharged to the environment. The water use cycle is a closed loop since water is conserved on our planet and consisting various stages: criteria-use-purification-standards-environment-criteria. We can no longer rely solely on the environment to absorb and treat the waste quantities of materials in our wastewater. To comply with effluent standards, the wastewater must be purified prior to its discharge [2]. Governmental bodies establish regulations setting standards for water discharge into the environment so that the criteria which have been set for reuse of that water can be met. Generally, those regulations are defined through parameters like soluble degradable organics [such as biochemical oxygen demand (BOD), chemical oxygen demand (COD), total organic carbon (TOC), and total oxygen demand] (Table 8.1) control the utilization or depletion of dissolved oxygen (DO) by the aerobic bacteria present in receiving streams or lakes. In setting standards

Table 8.1: Application of classical methods in analysis of water samples [3]. Parameters

Methods

Procedure

Volatile suspended solids Total solids Suspended solids Acidity Alkalinity Total hardness Carbonate hardness Chemical oxygen demand (COD) Biochemical oxygen demand (BOD) Oil and grease Residue chlorine Chlorides Sulphates Sulphides Cyanides Ammonia

Gravimetry Gravimetry Gravimetry Titrymetry Titrymetry Titrymetry Titrymetry Titrymetry Titrymetry Gravimetry Titrymetry Titrymetry Gravimetry Titrymetry Titrymetry Titrymetry

Drying in an oven Calcine in muffle furnace Filtration, drying, calcine Acid-base titration Acid-base titration Complexometric titration Acid-base titration Redox titration Redox titration Extraction, distillation Redox titration Precipitation titration Filtration, calcine, precipitation titration Distillation, redox titration Titration of the complex formation Distillation, acid-base titration

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for discharges, it is important to consider the concentration level of the pollutant and the flow rate of wastewater. A high flow rate can impose an unacceptable amount of pollutant on a receiving stream even if the concentration of pollutant is low. Percent removal is not an environmentally acceptable basis for setting standards. The total quantity as well as concentration of pollutant in the discharge should be controlled by the regulations. The water quality standards have legal backing and specify key characteristics for the water, dependent upon its intendent use. In conjunction with the specified tests and analyses a formal sampling protocol is also documented [2, 3]. Pollution of natural surface waters and groundwater by entering of unknown organic (pharmaceutics, pesticides and other organic substances) and inorganic constituents are increasing, how the number of inhabitants is increasing. At the same time, the consumption of potable water increases what caused requirements for better treatment of wastewaters. Namely, many wastewater treatment plants so far do not effectively remove all pollutants and become the main source of drinking water contamination. By recognizing the harmful effects of organic and inorganic pollutants, the requirements or standards to be met by quality drinking water are also changed. The increasingly stringent standards are also seeking to constantly improve the methods of processing but also the introduction of new modern procedures. For this reason, membrane processes have been increasingly used in practice, not only for the treatment of drinking water (sea, brackish and groundwater), but also for the treatment of wastewaters. In addition to the above-mentioned membrane processes, advanced oxidation processes (AOPs) are increasingly used, and classical water treatment methods are improved in accordance with established criteria and/or standards by scientific demand and government [2]. Drinking water treatment implies the most common pre-oxidation (aeration, chemical oxidation), polishing (removal of organic matter and micro-pollutants), disinfection, membrane processes, eliminating planktons and algal metabolites. Depending on the characteristics of raw water, specific treatments for removal of iron, manganese, ammonia, nitrates, hydrogen sulfide, arsenic, salinity, other metalloids and heavy metals, as well as organics should be applied. On the other hands, treatment of municipal or industrial wastewater is more and more demanding because the conventional methods of water treatment do not effectively remove socalled new pollutants like very small molecules of pharmaceuticals, pesticides and hormones. Therefore, it is essential to develop new methods of wastewater treatment (membrane processes, AOPs), to improve traditional or conventional methods, and to determine their effectiveness by monitoring pollutants removing after wastewater treatment with modern and highly sophisticated analytical techniques. In general terms the analytical methods used in the assessment of water and wastewater characteristics are very much the same irrespective of the ultimate purpose of the analysis. The choice of analytical method is often dictated by validation requirements such as detection limits, quantification limits, selectivity and sensitivity of methods

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[2, 3]. In the same time industry is the greatest user of water, so future industrial growth will be restricted to regions having adequate water supplies. The major industrial users of water are the primary manufacturers of metals, chemicals, papers, petroleum and food products. The pollutant concentrations in wastewater are often characterized by solid content and by BOD, which is a measure of the DO used by microorganisms in biological oxidation of organic matter. The total BOD of aqueous industrial wastes is three times the total BOD of wastes entering municipal wastewater treatment plants. Over 90 % of the industrial BOD is generated by the chemical, paper, food, and petroleum industries. The primary metals industry together with these four industries contributes 90 % of the solids entering industrial wastewater. The total solid entering sewage treatment plants from domestic wastes are less than one-half of the total solid in industrial wastes [2]. How life standards are progressing, demand for water accelerates. We have to meet the needs of an increasing world population by irrigating more of the unproductive areas and fulfilling the demands for an even greater industrial output. These needs require a stewardship of our water resources to preserve water quality through waste treatment and ensure adequate quantities through recycle. This means there is a pressing need to protect water and treat it, whether for the purpose of producing fresh water for human consumption, for specific industrial uses, or for limiting pollution discharged into the environment [1, 2]. The classification of water and wastewater depends on the type of measurements test that has to be performed. Thus, water characterization is carried out on the basis of biological, physical and chemical measurements [4]. 8.1.1 Biological characteristics Biological tests on water and wastewater determine whether pathogenic organisms are present by testing for certain indicator organisms. Biological information is needed to measure water quality for such uses as drinking and swimming, and to assess the degree of treatment of the wastewater before its discharge to the environment. Biological tests include testing on microorganisms which are classified as follows: animal (rotifers, crustaceans, worm, and larvae), plant (mosses and ferns) and protista (bacteria, algae, fungi and protozoa) [4]. 8.1.2 Physical characteristics The many properties of water which appeal to the natural senses are termed the physical characteristics. The most important physical characteristic of water is its solids content as it affects the esthetic, clarity, and color of the water. Other physical parameters are temperature and odors which are largely the result of baseline levels for that geographical area and are not commonly altered in a wastewater treatment plant [4].

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8.1.3 Chemical characteristics Nowadays environmental contamination is a recognized worldwide problem. Significant part of the environmental pollution is caused by application of pesticides in agriculture, horticulture and forestry, by emissions of hazardous chemical substances formed during industrial processes and combustion reactions. A large number of these compounds and/or their degradation products are highly toxic and they have negative effects not only on the ecosystem, but also on human health. In this context it is necessary to control the presence of organic pollutants in the environment, and at the same time, to assess the risk to human health due to the presence of the chemicals at workplace or in the environment in order to prevent adverse effects. The chemical characteristics of wastewater can adversely affect the environment in many different ways. Soluble organics can deplete oxygen levels in stream, and cause an unpleasant odor and taste of water supplies. Toxic substances affect on to the food chain and human health. Nutrients can cause eutrophication of lakes. Although some chemical tests are specific, many determine broad classifications due to the variety of compound found in wastewater [4]. Therefore, prior to processing of potable water and wastewater it is necessary to chemically characterize it, which implies determination of pH-values, temperature, conductivity, cation and anion analysis, DO and oxygen demand, TOC, determination inorganic and organic of pollutants. Determination of water parameters shown in the Table 8.1 are determined by classical analytical methods and these methods are the routine methods of each laboratory for water analysis. However, the determination of inorganic and organic pollutants may vary from water to water, especially in wastewater of industrial and municipal origin. Therefore, require the application of sophisticated analytical methods for the determination of inorganic and organic pollutants, especially if they are in trace amounts in water [3, 4]. Where water quality and characteristics are defined by regulation, the questions of what measurements to make, the methods to use, and the sampling protocol are clearly recorded. When carrying out surveys of environmental water for investigational or research purposes the situation is less clear cut. Clearly defined aims for the survey or investigation must be established before the appropriate methods can be selected. As stated earlier, chemical characterization also depends on the type of contamination whether it is inorganic or organic, and depending on it, different methods of analysis are also applied. Today, they are the biggest trace contamination problem because they require highly sophisticated analytical techniques that are often timeconsuming and costly for preparing analytical samples. Also, trace contaminations are difficult to remove by conventional methods of processing any water and wastewater.

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Before analyzing any sample, it should be in mind that each analysis is proceeded by sampling and sample preparation. Sampling, sample preparation and analysis procedures must be customized depending on whether the analyte is the main, minor component or trace component. The following section provides an overview about general analytical procedure for analysis of inorganic and organic trace pollutants in the environment. 8.1.3.1 Inorganic trace elements in water and wastewater A wide range of human activities contributes to the trace element pollution of the aquatic environment. The major activities include mining and ore processing, coal and fuel combustion, industrial processing (chemical, metal alloys, chloro-alkali and petroleum), agricultural (fertilizers, pesticides and herbicides) domestic and agricultural effluents or sewage, and nuclear activity. Elemental or heavy metal input can be from atmospheric fallout, leaching or dumping from the lithosphere, or directly into the aquatic environment (including ground, surface, river, lakes, estuarine, oceans, etc.). The impact of water pollution depends upon the value of trace element input, duration of input, physical and chemical form and associated ligands or chemicals. All of these inter-related factors will determine the elemental concentrations in the water system, and their relative availability, transport, and toxicity. The most important factor is the chemical form in which the element exists in solution. This depends upon pH, solubility, temperature, the nature of other chemical species, and many basic factors of solution chemistry. Many trace element contaminants entering the aquatic environment can have dramatic effects on the bioavailability and toxicity of biological processes. Prior to analyzing inorganic contaminants, especially the trace substances, representative sampling and good sample preparation are required. In general water sampling requires a very close inspection of the required procedures because most trace elements to be measured in water samples will be at very low or ultratrace levels (µg L−1 or ng L−1). Sample contamination and analyte losses are potential problems. Water samples can be collected from numerous sites from domestic faucet outlets to the effluents associated with industrial processes, and sewage or water treatment works. The frequency and duration of sampling is important in order to obtain both a representative and reproducible sample. It is common to take composite samples, which are composed of several individual samples taken at regular intervals. Various container pre-treatment procedures should be undertaken before sample collection. Only polyethylene or teflon vessels should be used. Prior to use all new containers should be washed and stored in ultra-pure grade 10 % HNO3 for 2 days, and rinsed with double distilled deionized water. All cleaned containers should be sealed in clean polypropylene bags until required. Acidification of the sample will reduce or eliminate trace element adsorption and hydrolysis. All water samples should be in theory analyzed immediately after collection. Most water

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samples require filtration immediately following collection with 0.45 or 0.50 µm membrane filters. All water samples should be stored in the dark, either by refrigeration (4 oC) or by deep-freezing (−20 oC). Long-term storage of frozen water samples may also be a problem for some trace metal species. Prior each water sampling, it is necessary to be well acquainted with sampling procedures depending on the requirements of the analyte which will be determined by one of the analytical methods. The ideal analytical technique for measuring trace elements generally in environmental samples must offer a very low detection limits, a wide linear dynamic range, simple interference-free data, qualitative, semiquantitative and quantitative analysis, possible simultaneous multielement capability, simple sample preparation, and high throughput and low cost per determination. In practice and in reality there is no ideal or universal analytical technique for environmental sample analysis. All the main contenders, including atomic absorption spectrometry (flame or electrothermal), atomic fluorescence spectrometry, inductively coupled plasma optical (or atomic) emission spectrometry, neutron activation analysis, X-ray fluorescence, proton-induced X-ray emission, spark source or isotope dilution mass spectrometry, electrochemical (anodic stripping voltammetry and polarography) or inductively coupled plasma-mass spectrometry have their advantages and disadvantages. The main limitations for most of these analytical methods are sensitivity or precision problems due to interferences and sample matrix effects. In conclusion, it is always important to remember that the trace element analysis of samples must be associated with an appropriate validation or quality control scheme. For the measurement of inorganic trace elements in water or wastewater samples the use of certified reference materials, or interlaboratory test comparison must always be undertaken and published along with the results of the study. 8.1.3.2 Organic trace elements in water and wastewater Environmental organic pollutants include aliphatic hydrocarbons, aromatic hydrocarbons, alcohols and phenols, anilines and benzidines, chlorinated solvents, polychlorinated biphenyls, pesticides (including insecticides and herbicides), and products used in the polymer industry such as phthalates and adipates, pharmaceuticals, pesticides etc. A detailed account of the analytical protocols used for the analysis of compound from each category is beyond the scope of this chapter; however, the importance of analytical procedures in the analysis of trace organic pollutants in the environment is emphasized here. The analysis of organic materials can be divided into two major classifications, the first being the identification of bulk materials, and the second the analysis of trace organic materials. The analysis of bulk materials is usually conducted on a single homogeneous component of known composition, and the procedure is one of identification, quantitation not usually being required. Techniques such as nuclear magnetic resonance and infrared (IR)

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spectroscopy which have been traditionally used as aids in identification rather than for quantitation are most applicable [3, 4]. Trace organic analysis is required where the components of interest are present at very low concentrations and contained within a bulk matrix that is often of an undetermined and heterogeneous composition. Consequently the methods used for the analysis of trace analytes are not as easily defined as for bulk organic materials. Physical separation (extraction and partition) of the analyte from the matrix is usually required before analysis can begin. Once achieved, further physical separation may be needed to remove interfering components from the extract that may have been co-extracted with the analytes. The presence of co-extractives interferes not only with analyte determination, but contributes to the fouling of chromatographic columns and detectors, and hence adversely affects the sensitivity and precision of analysis. Only after the analytes have been isolated can analysis proper begin. Where determination of a single analyte is required, direct spectroscopic methods of detection are favored as they can simply and quickly provide a means of positively identifying the analyte as well as enabling quantitation [3, 4]. Where several analytes have been isolated as a mixture, spectrometric and non-spectrometric physical detectors are used in conjunction with a variety of chromatographic techniques to enable quantitation. The combination of detectors and chromatographic techniques such as those commonly used for high performance liquid chromatography (HPLC) or gas chromatography (GC), are particularly suited to the analyses of multiresidue samples. Method commonly used for trace organic analysis can be assigned to one of three subdivisions: sample preparation, chromatography and detection [4]. Sample preparation is a necessary prerequisite for almost all trace organic analysis. The method of sample preparation is defined by the physical characteristics of the sample matrix and analytes, and phrase “like dissolves like” best describes the approach to successful analyte preparation. The method of sample preparation must also be compatible with chromatographic and associated detection systems that will be used later for analysis. In general, most protocols for sample preparation include several common steps which can be summarized as follows: maceration, dissolution, extraction, partition and concentration. Following sample preparation, isolation of individual analytes from a mixture can be achieved by highly efficient column chromatography [3, 4]. The diversity of trace organic compounds that have been found to contaminate water supplies has necessitated the development of many procedures for analysis. Statutory regulation of drinking water quality has meant that the ability to identify contaminants in µg L−1 or even ng L−1 concentration is required. Organic materials found in water can be placed into one of three classifications: volatile, semi-volatile and non-volatile compound. GC has been used for the analysis of volatile and some semi-volatile compounds. HPLC is ideally suited to the analysis of water samples, as a minimum of sample clean-up is required, and samples may be injected directly on

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column as aqueous solutions. HPLC is the method of choice for the analysis of semivolatile and non-volatile compounds. The Environmental Protection Agency (EPA) has published a series of bulletins for chromatographic analysis of trace organic priority pollutants in wastewater [4]. Direct analysis for trace components in water is often not practical, as the detection of species at very low concentrations would require extremely sensitive means detection, and would most certainly yield ambiguous results due to the presence of interfering compounds. Prior any analysis a concentration of analyte is generally required, where the concentrate must be enriched by at least a 100- and preferably a 1000-fold. For semi and non-volatile organic compound, liquid/liquid partition or solid phase adsorbents (SPE) are used extensively, especially SPE techniques are frequently used to trap and concentrate semi- and non-volatile organic materials from water and wastewater samples. Also, where GC is to be used for final analysis, analytes concentrated by SPE can be eluted by heating the extraction cartridge. If the cartridge has been mounted in line with the gas inlet to a chromatograph, then eluted analytes are swept directly onto the GC column for separation. Combined with mass spectrometry for identification, this purge and trap technique is a very powerful tool for the analysis of trace volatiles and semi-volatiles organic materials in water. When the HPLC system is combined with UV or fluorescent (FL) detector, transfer of the extract to solvents such as methanol and acetonitrile affords solvent compatibility with the mobile phase and detectors. Recently, for the purpose of analyzing semi-volatile and volatile organic pollutants in traces, mostly related chromatographic techniques are used with sophisticated detectors based on mass spectrometry (MS) [3, 4].

8.2 Water and wastewater treatment by membrane processes Membrane phenomena can be traced to the eighteenth century. French philosopher Abbé Nolet devised the word “osmosis” to describe permeation of water through a diaphragm in 1748 [5]. Osmosis is a natural process involving fluid flows across a semipermeable membrane. A breakthrough, as far as industrial membrane application were concerned, was achieved by the development of asymmetric membranes by Loeb and Sourirajan in 1962 [6]. In last few decades membrane processes are one of the fastest growing and fascinating fields in separation technology. These processes are capable of performing certain separation by use of a membrane. The main concept of the membrane processes is relatively simple but until now often unknown. Membrane (lat.: membrane = thin skin) might be described as a conventional filter but with much smaller pores and different in size to enable the separation of tiny particles, even molecules and ions [7]. A specific separation is accomplished by use of a membrane with the ability of transporting one component more readily than another. This means that the membrane is more permeable to certain components than other components because of differences in physical or

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chemical properties between membrane and the components that are transported through the membrane. Membrane processes are characterized by the fact that the feed stream, i. e. bulk solution, is divided into two streams, retentate and permeate, with different compositions as presented in Figure 8.1. Retentate stream (concentrate, brine) is the stream in which most particles, molecules or ions are retained by the membrane, while permeate is the one that passes through the membrane, containing much less solutes than in the feed stream. Both streams, retentate and permeate could be the product, i. e. if the aim of the separation is concentration, the retentate will be the product stream. However, in the case of purification mainly permeate is the desired product. Δp (5 — 40 bar)

a

FEED

b

polyamide active layer — selectivity (20—200 nm)

RETENTATE

MEMBRANE membrane

PERMEATE

polysulfone supporting sublayer — mechanical strength (40 μm) polyester fabric support— mechanical strength (100 μm)

Figure 8.1: Schematic presentation of (1) membrane cross flow process and (2) presentation of mass transport through thin film composite (TFC) membrane under pressure driving force [8].

Due to their multidisciplinary character membrane processes can be use in a large number of separation processes. Comparison between membrane processes and other separation processes is difficult but the main benefits of membrane processes are: separation can be carried out continuously, energy consumption is generally low, they can easily be combined with other separation processes (hybrid processes), separation can be carried out under mild conditions, up-scaling is easy, and they belong to the nondestructive and environmentally friendly processes. However, following drawbacks should be mentioned: membrane fouling, concentration polarization, and upscaling factor that is more or less linear [6]. It is important to mention that membrane fouling and concentration polarization should in fact not be considered as a disadvantage since these phenomena are inherently part of the separation process. Measures should be taken to reduce these phenomena as much as possible and this requires sufficient basic and application know-how. There are many membrane processes, based on different separation principles or mechanisms and specific problems can cover the broad size range from particles to molecules and ions. In spite of these various differences, all membrane processes have one thing in common, the membrane. Although it is difficult to give an exact definition

8.2 Water and wastewater treatment by membrane processes

251

of a membrane, a general definition could be: a selective barrier between two phases, the term “selective” being inherent to a membrane or a membrane process. It should be noted that this is a macroscopic definition while separation should be considered at the microscopic level. The definition says nothing about membrane structure or membrane function. The membrane is the heart of every membrane process and can be considered as a permselective barrier or interphase between two phases [6]. To accomplish particular separation and transport through the membrane a certain driving force on the feed stream has to be applied. In many cases the permeation rate through the membrane is proportional to the driving force, i. e. the flux-force relationship can be described by a linear phenomenological eq. (8.1): J= −A


dX ; dx

(8:1)

where A is called the phenomenological coefficient and dX/dx is the driving force expressed as the gradient of X (temperature, concentration, pressure and electric potential) along a coordinate x perpendicular to the transport barrier. According to the used driving force, pressure, activity (concentration), electrical potential, and temperature differences, membrane processes can be divided into pressure driven separations, concentration gradient membrane processes, thermally driven membrane processes, and electrically driven membrane processes, respectively. A general classification of membrane processes and technically relevant main membrane processes in water treatment are presented in Table 8.2. The next section will be focused on the pressure driven membrane processes, in which the flux through the membrane is induced by hydrostatic pressure difference between the feed and permaete stream (Figure 8.1) and depending of the value of applied pressure microfiltration (MF), ultrafiltration (UF), nanofiltration (NF) and reverse osmosis (RO) can be distinguish. The biggest difference between these processes, as go from MF to RO, is in the membrane pore size, and consequently, the size (or molecular weight) of the separated solutes diminishes. Due to membrane pore size decrease the driving force (pressure) has to be increased (0.1–2.0 bar, 1.0–5.0 bar, 5.0–20 bar, 10–60 bar for MF, UF, NF and RO, respectively), and on the other side permeability (L m−2 h−1 bar−1) decrease (>50, 10–50, 1.4–12, and 0.05–1.4, respectively). Pore size decrease, from MF to RO, effects on retention of various solutes in the water. Namely, viruses, proteins and bacteria are removed >99 % with UF, NF and RO, while small organic molecule and salts (ionic solids) are most completely (>99.9 %) retained by RO membranes which pore size are below 1 nm. The biggest differences can be seen between tight and loose NF membranes. For tight NF membrane monovalent and divalent ions are removed between 70% and 98 %, while for loose NF membranes monovalent ions are removed between 0 and 70 %, and divalent ions between 0 and 99 %. Due to its nondestructive character, membrane processes, in particular RO and NF, play a very important role in removing emerging pollutants

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Table 8.2: Technically relevant main membrane operations in water treatment [9]. Membrane process

Driving force

Microfiltration Ultrafiltration Nanofiltration

Pressure Pressure Pressure

Reverse osmosis

Pressure

Pervaporation

Activity (partial pressure) Activity (partial pressure) Activity (temperature) Activity (concentration) Electrical potential

Membrane stripping Membrane distillation Dialysis Electrodialysis

Mechanism of separation

Membrane structure

Phase 1

2

Macropores Mesopores Micropores

L L L

L L L

Sieve Sieve Sieve + (solution/diffusion + exclusion) Solution/diffusion + exclusion Solution-diffusion

Dense

L

L

Dense

L

G

Evaporation

Macropores

L

G

Evaporation

Macropores

L

L

Diffusion

Mesopores

L

L

Ion exchange

Ion exchange

L

L

from water and wastewater. Emerging contaminants are organic compounds, commercial products, used in large quantities in everyday life, such as pharmaceutically active compounds, endocrine disrupting compounds, pesticides, human and veterinary drugs, surfactants, textile dyes etc. The fundamental components of pressure membrane processes are the membrane chemistry (material) and the configuration into which the membrane is embedded. Membrane chemistry can be divided into organic (polymeric) and inorganic. Polymeric membranes are, at the moment, the most used membranes all over the world and they can be made from various polymers. First membrane, from 1960s, was made from cellulose (diacetate, triacetate). Significant number of polymers could be used for membranes but most frequent are aromatic polyamide (PA), polyacrylonitrile (PAN), polysulfone (PSf), polyethersulfone (PES), polytetrafluoroethylene (PTFE), polyvinylidenefluoride (PVDF), polyethylene (PE), polycarbonate (PC), and polypropylene (PP). In last few years great effort is invested in development of new generation membrane materials [10]. This includes nanocomposite, aquaporin, nanotube, and graphene-based membranes. The inorganic membranes are mainly ceramic made from Al, Zr and Ti oxide, nitrite, and carbides. These membranes possess high porosity, high permeability, defined pore size, and good mechanical properties, which make them suitable for use in wide range of application, such as water and wastewater treatment, medical and pharmaceutical, industrial processing, and food and beverage [11].

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253

There are two main parameters that describe the performance of efficiency of a given membrane; selectivity and the flux (J), or flow rate (Q) through the membrane. Flux is defined as the volume flowing through the membrane per unit area and time (L m−2 h−1) while for flow rate the unit is m3 d−1. The selectivity of a membrane toward a mixture can be expresses by the rejection (R) or the separation factor (α). The rejection factor is given by eq. (8.2): R=1−

γp γf

=

γf − γp γf

,

(8:2)

where γf and γp are concentrations of solute in feed and permeate, respectively. The value of R varies between 100 % (complete retention of solute; in this case we have an “ideal” semipermeable membrane) and 0 % (solute and solvent pass through the membrane freely) [6]. The basic membrane configurations (modules) that are used in commercial applications are hollow fiber, spiral wound, tubular, and plate-and-frame. Nevertheless, spiral wound and hollow fiber are widely used in modern water treatment applications. In industrial practice, it is possible to connect up to seven spiral modules in the one pressure vessel without causing a significant drop in pressure (see Example 8.1). The main application of pressure driven membrane processes, especially RO, is sea water desalination and brackish water treatment. The largest RO desalination plants are installed in Israel (Sorek, Hadera, Ashkelon) with a capacity of 420,000, 355,000 and 325,000 m3 d−1 respectively, and in Europe (Barcelona, 200,000 m3 d−1). The price of so-obtained drinking water is 0.5–0.6 $ m−3. If the other processes are included, together with development of new membranes, application is involved in almost all industries (textile, food and beverage, pulp and paper, power industries, etc.) [12]. It is assumed that application of pressure membrane processes will rise since the global membranes market for the 5-year period 2016–2021 is projected to reach 11.95 billion USD by 2021 [11].

Example 8.1. Calculation of the rejection factor and recovery. In the diagram are given fluxes and concentrations in feed, retentate, and permeate. According to the presented data calculate rejection and recovery.

Qf = 100 m3 d-1

Qr = 25 m3 d-1

γf = 4000 mg L-1

γf = 15400 mg L-1

Qp = 75 m3 d-1 γp = 200 mg L-1

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8 Water and wastewater treatment engineering

Recovery: ðγ − γ Þ It can be calculated through flow rate (or flux) and concentrations: Y = Qp = Jp =
r f  Jf γr − γp Qf Qp 75 m3 d − 1 Flow rate: Y = = = 0:75
100% = 75% Qf 100 m3 d − 1   γr − γf ð15400 − 4000Þ mg L − 1 11400 = Concentrations: Y =  = = 0:75
100% = 75% 15200 ð15400 − 200Þ mg L − 1 γr − γ p Rejection: R=

γf − γ p γf

=

4000 mg L − 1 − 200 mg L − 1 = 0:95
100% = 95% 4000 mg L − 1

Example 8.2. Selection of the module and calculation of technical conditions of membrane process for treatment of surface water to produce drinking water. The goal is to find optimal membrane treatment to decrease concentrations of dissolved organic carbon (DOC) and hardness of water (γ(Ca)) using 7 membrane modules in a vessel. Concentration of DOC in surface water was 7 mg L−1 and γ(Ca) = 140 mg L−1. After the treatment DOC has to be 4.2 mg L−1 and γ(Ca) = 60 mg L−1. In Table 8.3 the manufacturers’ data for typical RO and NF modules are given. Qf

Qr

γf

γr Qp1 γp1

Qp2 γp2

Qp3 γp3

Qp4 γp4

Qp5 γp5

Qp6 γp6

Qp7 γp7

Table 8.3: The manufacturers’ data for typical RO and NF modules.

3

−1

Qp/[m d ] p/[bar] RDOC RCa Y A/[m2]

RO1

RO2

NF1

NF2

44.0 10.2 0.96 0.99 0.15 37.0

41.0 10.2 0.96 0.99 0.10 30.7

33.0 7.0 0.946 0.946 0.15 37.0

27.7 5.5 0.95 0.45 0.15 37.0

For membrane water treatment, depending on quality and quantity of feed water, it is necessary to choose membrane module. From technical data of membrane modules it is possible to calculate number of modules for treatment of certain amount of water. According to the Table 8.3 differences between RO and NF membranes are visible. For the first calculation NF1 membrane will be used due to lower pressure compared to RO membranes and higher RCa than NF2. Main parameters for calculation of module characteristics are recovery (Y), working pressure p, rejection factors of dissolved solutes R, permeate flow rate Qp, and concentration of solutes in the feed which is necessary to decrease. Recovery for one module is 0.15 while concentration of feed and

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255

working pressure changes in pressure vessel from first to last module. This is due to increase of feed concentration and low decrease of pressure in each module. Permeate and retentate flow rate can be calculated: 1. module – permeate flow rate: Qp1 = 0:15
220 = 33:0 m3 d − 1 retentate flow rate: Qr1 = Qf 1 − Qp1 = 220:0 − 33:0 = 187:0 m3 d − 1 5. module – permeate flow rate: Qp5 = 0:14
116:3 = 16:3 m3 d − 1 retentate flow rate: Qr5 = 116:3 − 16:3 = 100:0 m3 d − 1 The same way is for calculating for all other modules and results are presented in Table 8.4. Qp = 146 m3 d − 1

Table 8.4: Calculation of flow rate in the pressure vessel of the process containing seven NF1 modules. p = 7 bar, Qp = 33.0 m3 d−1, R = 0.946. Module 1 2 3 4 5 6 7

Qf/[m3 d−1]

Y

Qr/[m3 d−1]

Qp/[m3 d−1]

220.0 187.0 159.0 135.2 116.3 100.0 86.0

0.15 0.15 0.15 0.14 0.14 0.14 0.14

187.0 159.0 135.2 116.3 100.0 86.0 74.0

33.0 28.0 23.8 18.9 16.3 14.0 12.0

Next step is calculation of DOC and Ca concentrations in permeates and retentate for each module. The water mass balance for a membrane element is given by: Qf = Qp + Qr . Also, the dissolved material of mass balance can be derived by: Qf γf = Qp γp + Qr γr . Therefore, concentration of DOC in module 1 retentate is: γr1 =

Qf γf − Qp γp Qr

=

220
7:0 − 33
0:38 = 8:17 mg L − 1 187

All concentration of DOC and Ca are calculated on the same basic and concentrations are presented in Table 8.5.

Table 8.5: Calculation of concentrations in the pressure vessel of the process containing seven NF1 modules. p = 7 bar, γf,DOC = 7 mg L−1, γf,Ca = 140 mg L−1, R = 0.946. Module 1 2 3 4 5 6 7

γf,DOC [mg L−1]

γr,DOC [mg L−1]

γp,DOC [mg L−1]

γf,Ca [mg L−1]

γr,Ca [mg L−1]

γp,Ca [mg L−1]

7.00 8.17 9.53 11.12 12.83 14.81 17.09

8.17 9.53 11.12 12.83 14.81 17.09 19.72

0.38 0.44 0.51 0.60 0.69 0.80 0.92

140.0 163.6 190.9 222.8 260.0 300.0 346.3

163.6 190.9 222.8 260.0 300.0 346.3 399.6

7.6 8.8 10.3 12.0 14.0 16.2 18.7

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8 Water and wastewater treatment engineering

As seen in Table 8.5, a concentrations of DOC and Ca in all permeates are different. If permeates are collected together average concentrations of DOC and Ca can be calculated. Results are: γp,DOC = 0.62 mg L−1 DOC and γp,Ca = 12.5 mg L−1Ca. Overall recovery can be calculated: Y =

Qp 146 m3 d − 1 = = 0:664
100% = 66:4%. Qf 220 m3 d − 1

8.3 Biological wastewater treatment Biological treatment is one of the most widely used methods for organic matter removal as well as for partial or complete stabilization of biologically degradable substances in wastewaters. Biological unit processes involve microbial activity, which is responsible for organic matter degradation and removal of nutrients. Microorganisms require energy for respiration and organic carbon food sources (COHNS) in order to synthesize new cells (C5H7NO2). Metabolic reactions, occurring within a biological treatment process, can be divided into three phases: organic matter oxidation, cell material synthesis and endogenous respiration or cell material oxidation. The three phases are [13, 14]: Oxidation : COHNS + O2 + bacteria ! CO2 + H2 O + NH3 + other end product + energy Synthesis : COHNS + O2 + bacteria ! C5 H7 NO2 Endogenous respiration : C5 H7 NO2 ! 5CO2 + 2H2 O + 4NH3 The primary objective of biological wastewater treatment processes is conversion of biodegradable organics into a microbial biomass. Organic pollutants are defined by three common parameters: BOD, COD and TOC. Table 8.6 shows the typical concentrations (mg L−1) of organics found in untreated domestic wastewater [13]. Table 8.6: Typical composition of untreated domestic wastewater. Constituents

−1

BOD/[mg L ] COD/[mg L−1] TOC/[mg L−1]

Typical concentration Low

Medium

High

110 250 80

190 430 140

350 800 260

BOD is used commonly as an indirect measure of organic matter and it represents the amount of oxygen utilized by microorganisms to biologically oxidize organic compounds in aerobic conditions in the dark at 20 °C over a period of 5 days. Five days as

8.3 Biological wastewater treatment

257

the representative period is assumed to determine the characteristic of BOD. The COD is the amount of oxygen necessary to oxidize organic compounds chemically. The COD test is used to determine the oxygen equivalent of the organic matter that can be oxidized by a strong chemical oxidizing agent (potassium dichromate) in an acid medium. Typical values for the ratio of BOD/COD for untreated municipal wastewater, as reported in Table 8.7, are in the range from 0.3 to 0.8 [13]. This ratio has been commonly used as an indicator for biodegradation capacity and is called biodegradability index. If the COD value is much higher than the BOD value, the sample contains large amounts of organic compounds that are not easily degradable. If the BOD/COD ratio for untreated wastewater is 0.5 or greater, the waste is considered to be easily treatable by biological means. If the ratio is below about 0.3, either the waste may have some toxic components or acclimated microorganisms may be required in its stabilization. TOC represents the TOC in organic compounds and independent of oxidation state of organic matter. The corresponding BOD/TOC ratio for untreated wastewater varies from 1.2 to 2.0. In using these ratios it important to remember that they will change significantly with the degree of treatment the waste has undergone [13–15]. Table 8.7: Comparison of ratios of various parameters used to characterize wastewater. Type of wastewater Untreated After primary settling Final effluent

BOD/COD

BOD/TOC

0.3–0.8 0.4–0.6 0.1–0.3

1.2–2.0 0.8–1.2 0.2–0.5

Example 8.3. What is the relationship between the BOD and COD values in wastewater? To establish the BOD/COD ratio for your wastewater, simply have both COD and BOD run on several wastewater samples. Divide the BOD concentration by the COD concentration for each sample and average the results. For example, below is the BOD/COD ratio developed using three wastewater samples: Sample 1 : BOD = 183 mg L − 1 ; COD = 352 mg L − 1 : BOD=COD = 183=352 = 0:52 Sample 2 : BOD = 172 mg L − 1 ; COD = 358 mg L − 1 : BOD=COD = 173=342 = 0:48 Sample 1 : BOD = 165 mg L − 1 ; COD = 340 mg L − 1 : BOD=COD = 175=350 = 0:49 BOD=COD = ð0:52 + 0:48 + 0:49Þ=3 = 0:50 Explanation: The BOD/COD ratio has been used as one of the well-adopted surrogates for biodegradability of TOC. This ratio varies with the wastewater and degree of treatment. If BOD/ COD ratio is > 0.5 than easily biodegradable 0.4–0.5 average biodegradable, 0.2–0.4 slowly

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8 Water and wastewater treatment engineering

biodegradable, and < 0.2 not biodegradable. If the BOD/COD ratio is small, the reason can be toxicity, low biodegradability or both together, which results in inhibition of metabolic activity of microorganisms. COD test for both (biodegradable and non-biodegradable) using chemical oxidizing agent, while BOD test is only for (biodegradable) using bacteria. For that reason COD is always higher than BOD.

8.3.1 Activated sludge process Biological wastewater treatment has been utilized globally for decades. There are many different processes that vary depending on the origin of wastewater, i. e. the existing contamination. Still, one of the most frequently used process is biological wastewater treatment with activated sludge, because of its effectiveness in treatment of wastewater. The activated sludge process is a complex biological system in which organic matter is removed from wastewater by aerobic microorganisms. The microorganisms are incorporated within or on floc of activated sludge and aeration of wastewater suspension ensures the exchange of products of metabolism and substrates, as well as the oxygen required to maintain aerobic respiration and catabolic reactions. In the activated sludge process the incoming wastewater is mixed and aerated with existing activated sludge (microorganisms). Aerobic oxidation of organic matter is carried out in aeration tank. The content of the aeration tank in an activated sludge system is called mixed liquor. The mixed liquor suspended solids (MLSS) is the total amount of organic and mineral suspended solids, including microorganisms, in the mixed liquor. Organics in the wastewater come into contact with the microorganisms and are utilized as food and oxidized to CO2, H2O, NH4, and new cell biomass. As the microorganisms use the organics as food they reproduce, grow, and die. The organic portion of MLSS is represented by mixed liquor volatile suspended solids (MLVSS), which comprises non-microbial organic matter as well as dead and live microorganisms. The MLVSS/MLSS ratio is typically in the range 0.65– 0.85. Primary effluent is introduced and mixed with return activated sludge to form the mixed liquor, which contains 1500–3000 mg L−1 of suspended solids. The aeration tank is provided with fine bubble diffused aeration pipework at the bottom to transfer required oxygen to the biomass and also ensure completely mixed reactor. An important characteristic of the activated sludge process is the recycling of a portion of the biomass. This practice helps to maintain an activity of microorganisms in effectiveness of oxidizing organic compounds in a relatively short time. The detention time in the aeration basin varies between 4 and 8 h. The aeration tank is a completely mixed bioreactor where specific concentration of biomass is maintained along with sufficient DO concentration (typically 2 mg L−1) to effect biodegradation of soluble organic impurities measured as BOD or COD. Excess biomass is wasted to the sludge handling and dewatering facility [14–16]. The purification process occurs in two steps: transformation of the solved and particular wastewater contents to

8.3 Biological wastewater treatment

259

activated sludge and separation of the activated sludge from cleaned wastewater through sedimentation. Separation of the activated sludge is possible because of the formation of the activated sludge flocs [15]. The characteristic schematic layout of activated sludge process is shown in Figure 8.2.

PRIMARY EFFLUENT

AERATION TANK

RETURN ACTIVATED SLUDGE (RAS)

FINAL CLARIFIER

EFFLUENT

EXCESS SLUDGE

Figure 8.2: Conventional activated sludge system.

8.3.2 Environmental factors Environmental factors which influence biological growth include temperature, pH, mixing intensity, the presence of DO, and the food/microorganism ratio, F/M [14, 16]. Temperature is an important factor that can affect biological activity. Both temperature and pH have an important effect on the survival and growth of microorganisms. If the temperature gets higher or lower, then the process is functioning less efficiently. Because of these increasing temperatures, the possible amounts of DO in water decrease, and this occurrence has a negative influence on the efficiency of the aerobic treatment system. The pH-level is an important factor of biological wastewater treatment. Low pH-values may inhibit the growth of nitrifying organisms, while the growth of filamentous organisms is encouraged. Optimal pH range for microbial growth is between 6 and 9. It is the sudden change in pH that the most upsets microbial metabolism. Mixing is important to ensure effective contact between the active microorganisms and the organic matter, and to prevent accumulation of products of microbial decomposition. During oxidative biodegradation, microorganisms consume oxygen. DO concentration in aerobically treated wastewater is maintained at a certain adjusted level. Concentrations lower than 2 mg L−1 must be prevented since such a low concentrations may induce simultaneous anaerobic processes. The F/M ratio is a measure of the food entering the activated sludge process and the microorganisms in the aeration tank and it is expressed in kilogram BOD per kilogram of MLSS per day. The F/M ratio tells us something about growth and cell condition. If the F/M ratio is high, the growth is normally quite rapid (because this means there is a lot of “food” available in comparison to the amount of microorganism); if the F/M ratio is low, the growth is normally very slow (because little food is available for growth).

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8.3.3 Membrane bioreactor Activated sludge process is characterized by reliable operation and flexible capacity. However, when requirements for a higher effluent quality are imposed, activated sludge process must be expanded and additional purification procedures added. In recent years, new membranes that have been specially developed for use in wastewater treatment, made the membrane bioreactors application a promising alternative to the aerobic processes. The combination of an aeration tank and membrane filtration unit for the separation of activated sludge is defined as the membrane-coupled activated sludge process. Consequently, the difference from the conventional activated sludge process lies only in the separation of the activated sludge. Ultra- or micro-filtration membrane possesses advantage in possible replacing conventional sedimentation for the separation of the treated water from the sludge. The use of submerged membranes has reduced the power consumption of membrane bioreactors and hence increased their potential for the application of membranes in wastewater treatment. The complete retention of activated sludge allows operation at much higher biomass concentrations [16, 17].

8.3.4 Biology of activated sludge Activated sludge system is an aerobic biological wastewater treatment process which contains mixed culture of microorganisms. It is a complex and variable heterogeneous suspension containing both feedwater components, metabolites produced during the biological reactions and biomass. In the biological oxidation of wastewater, both synthesis and oxidation occur. Many groups of activated sludge microorganisms take part in carrying out the process. In an activated sludge system that is properly operated, biological flocs are produced that incorporate most of the important groups of microorganisms. Bacteria, fungi, algae, protozoa, and metazoan constitute the biological component, or biological mass, of activated sludge. The population active in a biological wastewater treatment is mixed, complex and interrelated. In general, the bacteria in the activated sludge process seemed to be gram-negative and include members of the genera Pseudomonas, Zoogloea, Achromobacter, Flavobacterium, Nocardia, Bdellovibrio, Mycobacterium, and the two nitrifying bacteria, Nitrosomonas and Nitrobacter. Additionally, various filamentous forms, such as Sphaerotilus, Beggiatoa, Thiothrix, Geotrichum, may also be present. In the normal operation of the activated sludge plants, the bacteria are shaped in a floc form. In fact not all microorganisms in activated sludge mixed-liquor are beneficial. Filamentous organisms cause swelling of floc by increasing the water content of the bacterial cell. Under this condition the floc particle will have similar density as the water itself and particles will not settle efficiently. This type of sludge is called bulking sludge. The species of microorganism that dominates in a system depends

8.3 Biological wastewater treatment

261

on environmental conditions, process design, the mode of treatment plant operation, and the characteristics of the wastewater. Floc structure, like size and morphology, plays an important role in determining the efficiency and economics of the activated sludge process [14]. Figure 8.3 present microphotographs of aerobic flocs without/ with and filamentous bacteria.

Figure 8.3: Microphotographs of flocs, and flocs with filamentous bacteria, M = 100× .

Protozoa are significant predators of bacteria in activated sludge as well as in natural aquatic environments and indicators of biomass health and effluent quality. Protozoa have an important role in maintaining a good balance in the biological ecosystem: they eliminate the excess bacteria and stimulate their growth and they promote flocculation (Figure 8.4).

Figure 8.4: Microphotographs of flocs and protozoa, M = 100× . Microphotographs were taken at Faculty of Chemical Engineering and Technology, University of Zagreb, Department of Industrial Ecology.

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8.3.5 The Monod equation The Monod equation [15, 16] assumes that the rate of biomass production is limited by the rate of enzyme reactions involving utilization of the substrate compound that is in shortest supply relative to its need. Equation (8.3) shows this relationship, S (8:3) μ = μmax
Ks + S where µ represents specific growth rate, 1/d; µmax represents the maximum specific growth rate, 1/d S represents substrate concentration, g L−1; Ks is the substrate saturation constant, g L−1, defined as the concentration of substrate at half the maximum specific growth rate. The biodegradation process results in microbial growth with the removal of substrate. Substrate concentration decreases with the growth of microorganisms. Therefore, the following equation can be developed: rs =

1 μmax Xv S Y Ks + S

(8:4)

where rs is substrate consumption rate, g L−1 d−1; Y is the growth yield coefficient, g/g; Xv is biomass concentration, mg L−1. The carbon and energy source, measured as COD, is usually considered to be the growth-limiting substrate in biological wastewater treatment processes. MLVSS represents the concentration of biomass in activated sludge. Microbial growth rate can be described by eq. (8.5): rx =

μmax Xv S − kd Xv Ks + S

(8:5)

where rx is biomass growth rate, g L−1 d−1; and kd is the decay coefficient, 1/d. Cell concentration reduction is known as endogenous respiration stage. Example 8.4. Write the linearized Monod’s equation and show its graph. How would you calculate the μmax and Ks? Monod’s equation can be linearized using the Lineweaver–Burke equation: 1 KS 1
= μ μmax μmax 1/μ

Graph shows a plot of 1/μ vs. 1/S. The

Slope = Ks/μmax

slope, y-intercept, and x-intercept are (KS/μmax), (1/μmax), and (−1/KS), respec1/μmax

tively. This plot allows the computation of KS and μmax. -1/Ks

1/S

8.4 Advanced oxidation processes

263

8.4 Advanced oxidation processes There are varieties of (waste)water chemical treatment methods based on the application of strong oxidants or in situ generation of oxidizing species. However, their constrains related to their chemistry, which may lead to the production of harmful byproducts, as well as the reactivity and selectivity toward targeted pollutants, may provide significant implications at larger scale and should be taken into account when considering appropriate treatment method for the removal of organic, particularly recalcitrant, pollutants [18]. Accordingly, in last two – three decades, advances in chemical treatment of water and wastewater resulted with the development of a numerous alternative chemical technologies; so-called AOPs. The interest of scientific community and water professionals rapidly increased for the development and application of AOPs as (waste)water treatment methods, yielding numerous scientific publications as well as designs and applications on full-scale treatment facilities [18]. The technologies based on AOPs may offer viable solution for the treatment of (waste)waters of different origin. One of the main advantage of AOPs over conventional biological, physical-mechanical and chemical (waste)water treatment processes is capability to degrade wide range of organic pollutants into the less harmful or biodegradable byproducts, and eventually convert them into CO2, H2O and inorganic ions [19]. Besides, AOPs are considered as low- or even none-waste generation technologies [20], thus secondary treatment is avoided. The principle mechanism of AOPs is based on the in situ generation of highly reactive transient radical species that readily attack various recalcitrant organic pollutants, kill waterborne pathogens, and break down disinfection byproducts. Hydroxyl radicals (E°(HO•) = 2.80 V), are considered to be the main reactive species possessing high reactivity (Table 8.8) and non-selectivity toward organics [21].

Table 8.8: Standard redox potential of some oxidant species [22]. Oxidant Flour Hydroxyl radical Sulphate radical Atomic oxygen Ozone Persulfates Hydrogen peroxide Permanganate ion Chlorine Chlorine dioxide

Redox potential, E°, V 3.03 2.80 2.60 2.42 2.07 2.01 1.77 1.67 1.36 1.27

AOPs demonstrated high flexibility in practical application; thus can be used either separately or in combination, or in combination with other traditional wastewater

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treatment methods. Although the total mineralization of organic structures might be achieved by AOPs, such task could be sometimes very costly. Hence, AOPs may serve as an effective tool for converting non- or low-biodegradable organics to more readily biodegradable intermediates [23]. Accordingly, AOPs might precede secondary (biological) treatment in to increase increasing biodegradability and lowering toxicity, i. e. to destruct recalcitrant chemical structures, or can be used as tertiary treatment in order to remove remained organics upon secondary treatment. AOPs possess great advantage over common traditional (waste)water treatment methods; they can be conducted at ambient conditions, i. e. atmospheric pressure and room temperature. AOPs can be effectively used for the treatment of low to moderately loaded wastewaters; with organic content expressed by the means of TOC in range of 100–1000 mgC L−1 [24]. For highly loaded wastewaters, with COD values over 3–5 g L−1, other wastewater treatment processes also generating OH radicals can be used. Although some authors consider such processes as AOPs, these processes, including wet air oxidation, supercritical wet air oxidation and other hydrothermal oxidation processes requiring pressure and temperature highly over ambient conditions (even above 1 MPa and 150 °C), can be classified as nonambient AOPs [22, 24]. Generally, HO• can be generated, by chemical, electrical, mechanical or radiation energy. Thus, AOPs can be classified into chemical, electrical, mechanical and photoassisted processes. Chemical AOPs include Fenton-based processes, involving the application of transitions ions (mostly iron) combined with strong oxidants (hydrogen peroxide or persulfate salts), as well as ozone-based processes, involving various combinations of catalytic ozonations and peroxone processes combining two or more oxidants. Photo-assisted AOPs include various photochemical processes, involving the application of UV irradiation sources with powerful oxidant (ozone, hydrogen peroxide and/or persulfate salts), and photocatalytic processes, involving the application of UV or solar energy and various semiconducting materials as photocatalyst. These two groups of AOPs are mostly investigated and are operating at larger scales to treat various types of wastewater, thus are discussed further in more details. 8.4.1 Chemical AOPs 8.4.1.1 Fenton-based processes The processes involving catalytic reaction between transition metal ions and hydrogen peroxide (H2O2) can be classified under Fenton-based processes. The reactivity of such system was firstly observed by Fenton in 1876 [25, 26], applying iron in a form Fe2+ ions and H2O2. Upon more detailed research focused on the undergoing mechanism generating HO• within such system in 1930s, the application of Fenton process for the degradation of various classes and types of organic pollutants in water is continuously growing and is expanded into large-scale applications. The reactivity of Fenton process is based on reaction that involves

8.4 Advanced oxidation processes

265

oxidation of Fe2+ ions to Fe3+ ions with H2O2 and subsequent generation of HO•, as demonstrated by eq. (8.6): Fe2 + + H2 O2 ! Fe3 + + HO  + HO −

(8:6)

The generated HO• would undergo reaction with present organics within water matrix. The above given reaction (6) is often considered as Fenton reaction [27], however it represents only first, but key step in the Fenton process. The so-called Fenton catalytic cycle involves following reactions eqs. (8.7)–(8.13) as well, describing iron recovery and quenching within the system and reacting mechanism responsible for degradations of present organics (RH). Fe2 + + HO  ! Fe3 + + HO −

(8:7)

Fe3 + + H2 O2 ! Fe2 + + HO2  + H +

(8:8)

Fe2 + + HO2  ! Fe3 + + HO2−

(8:9)

Fe3 + + HO2  ! Fe2 + + O2 + H +

(8:10)

RH + HO  ! H2 O + R 

(8:11)

R  + Fe3 + ! Fe2 + + products

(8:12)

R − COO − + Fe3 + ! Fe3 + − complex

(8:13)

The formed by-products through reaction eq. (8.12) undergo further degradation through radical mechanism up to complete mineralization forming eventually CO2 and H2O [28]. The reaction eq. (8.13) describing the tendency of ferric ions (Fe3+) to form organic complexes with carboxylates [29], demonstrates quenching of iron from Fenton catalytic cycle, and is rate limiting for the overall process effectiveness due to restraining the iron recovery and causing lack of HO• within the system. Fenton-based processes include systems with similar reaction chemistry that apply alternative catalysts instead of homogeneous ferrous iron for the incitation of Fenton reaction; (i) ferric salts, (ii) heterogeneous iron-based materials including: iron powder, iron-oxides, iron-ligands, or iron ions doped in zeolites, pillared clays or resins, and (iii) other metal ions, e. g. copper, manganese or cobalt [21, 27, 30]. Lately, besides alternative catalyst in Fenton-based processes, the alternative oxidant is also investigated. Thus, persulfates (usually in form of Na+, K+ and NH4+

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salts), characterized by high solubility and stability at the ambient temperature, was found to effective alternative to H2O2. The persulfate anion, S2O82- is a strong oxidant (Table 8.8) that can be easily activated by transition metals (M) (or by heat or UV irradiation) to generate highly reactive sulfate radical, SO4-• eq. (8.14) that is also unselective, while the sulfate ions, as major products of persulfate reduction, can be considered as relatively harmless and environmentally friendly [31]. S2 O28 − + M2 + ! M3 + + SO 4− + SO24 −

(8:14)

However, it should be noted that iron (or transition metal) in persulfate reduction, described by above reaction, does not have catalyst role, but it acts as activator; i. e. it can not be recovered as in Fenton catalytic cycle [31]. The primary benefits of Fenton-based processes, besides the ability to convert a vast array of organics into harmless and/or biodegradable products, are relatively cheap reagents that are ease and safe to handle, and are moreover environmentally benign [27]. However, the effectiveness is constrained by following disadvantages: (i) the necessity to remove remaining iron ions after the treatment, and (ii) aforementioned quenching of ferric ions into stable complexes [27], that can be overcome by the usage of alternative heterogeneous catalyst mentioned above and UV- or solar-assisted systems enabling the destruction of formed Fe3+-complexes and continuous involvement of iron ions into the Fenton cycle [29]. One should be aware that Fenton-based processes are multi-factor systems, and that effectiveness strongly depends on key operating parameters: (i) iron concentration, (ii) source of (iron) catalysts, H2O2 (or S2O82-) concentration, catalysts/oxidant ratio (so-called Fenton reagent), temperature, pH and treatment time [21, 27]. Accordingly, the minimal threshold concentration of ferrous ions allowing Fenton reaction to occur ranges between 3 and 15 mg L−1, however, iron levels >> 18.6 dm3 mol−1 cm−11), resulting with almost 1000 times higher rate of photolysis yielding H2O2 eq. (8.29) formation, that undergo further decomposition according to eq. (26): O3 + H2 O ! H2 O2 + O2

(8:29)

Such oxidative system can be considered as multi-beneficiary regarding mechanisms involved in HO• generation; (i) through H2O2 photolysis eq. (8.26) and (ii) through peroxone chemistry eq. (8.24), and degradation of organics; (i) direct photolysis, (ii) HO• attack and (iii) direct ozonation [21]. As most of AOPs, photochemical processes are multi-factor systems; the effectiveness strongly depends on the process parameters related to both reactor design and characteristics of reaction mixtures. Hence, parameters that need to be optimized through reactor geometry are effective length path and flow regime, while characteristics of irradiation source are directly related to the radiant power and irradiation wavelength. The operating parameters such as pH, oxidant type and concentration would dictate the quantity of formed radical species and need to be optimized as well. Besides, constrains of photochemical processes are related to the presence of suspended matter, lowering solution transparence, and various species (e. g. counter ions), providing scavenging effect toward generated radical species.

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8.4.2.2 Photocatalytic processes Heterogeneous photocatalysis, employing semiconductor (nano)particles such as TiO2, ZnO, Fe2O3, CdS, ZnS, SnS2, and many others, is based on the photonic excitation of a solid. Underlying mechanism includes following phenomena, and is presented through eqs (8.30)–(8.34). Upon illumination of semiconductor (nano)particle by efficient energy electrons from valence band would cross the gap to be transferred into the conductance band, creating the electron-hole (e–h+) pair at the semiconductor (nano) particle surface. Such photogenerated electrons could react with adsorbed electron acceptor species, while the holes react with electron donor species, creating reduced and oxidized products, respectively. Accordingly, in the case of polluted water, electron acceptor specie is DO, resulting with superoxide radical (O2•-) formation or its protonated form (HO2•). The electron donor specie could be either (i) water (or hydroxyl ion), resulting with the formation of hydroxyl radicals (HO•) capable to degrade organics, or (ii) pollutant molecule itself (usually organic specie; commonly marked as RH), which can be directly degraded through the formation of its radical by-product [34]. The most common semiconducting material applied in photocatalytic water treatment titanium dioxide (TiO2); it has been promoted due to the: (i) high photocatalytic activity under the incident photon wavelength of 300 nm < λ < 390 nm and stability in consecutive catalytic cycles, and (ii) multi-faceted functional properties of TiO2 catalyst, such as chemical and thermal stability, resistance to chemical breakdown and attractive mechanical properties [35]. hν

+ − + eCB TiO2 ! hVB

(8:30)

+ ! HO  + H + H2 O + hVB

(8:31)

+ R + hVB ! R+

(8:32)

− ! O2−  O2 + eCB

(8:33)

O2−  + 2H + $ 2HO2 

(8:34)

However, the application of TiO2 (nano)catalysts for water treatment is still experiencing a series of technical challenges. The separation of (nano)particles after water treatment remains the major disadvantage for commercial purposes. The fine particle size of the TiO2 powders, and their large surface area-to-volume ratio and surface energy, creates a strong tendency for agglomeration during the operation, being highly detrimental in views of particle size preservation, surface-area reduction and its reusable lifespan. Other technical challenges include the limitation of TiO2 to absorb irradiation energy in broader incident radiation range and its integration with feasible photocatalytic reactor systems [35, 36]. Hence, current research is directed to

8.4 Advanced oxidation processes

271

the immobilization of semiconducting materials on various supports in order to avoid in-treatment agglomeration and posttreatment separation issues and catalyst modification in order to enlarge its “narrow” wavelength spectrum for photoactivation, which can improve the overall light utilization properties. Such harvesting a broader spectrum of solar irradiation involves lowering of the band gap of semiconducting material, while inhibiting the recombination of photogenerated charges. Strategies including doping with non-metals, incorporation or deposition of noble metals (ions), and material engineering solutions based on composites formation using transition metals, carbon nanotubes, dye sensitizers, conductive polymers, graphene (oxide) and semiconducting materials, present viable solutions for set tasks [37]. 8.4.3 Reactions and kinetics of hydroxyl radicals According its mechanism, the reactions of HO• with organics can be classified within three groups [38]: i. Electrophilic addition of HO• on double bond: H

.

+ OH

OH

.

ii. Abstraction of hydrogen atom: R − H + HO  ! R  + H2 O

(8:35)

R − H + HO  !ðR − HÞ  + HO −

(8:36)

iii. Electron transfer:

All three mechanism yield initial radical product, while further reactions result in the formation of non-radical products; e. g. alcohols, aldehydes, carboxylic acids, ketones, dimers, and eventually final mineralization products CO2 and H2O. Regardless the occurring mechanism presented above, the general reaction of HO• with organic pollutant (P) can be presented as: HO  + P ! products

(8:37)

while the rate of reaction is given by: r= −

dcP = kHO; P  cHO  cP dt

(8:38)

where kHO;M stands for reaction rate constant between HO• and targeted organic pollutant.

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8 Water and wastewater treatment engineering

Considering the fact that the concentration of organic pollutant (P) is significantly higher than the concentration of HO• (cP  cHO ), the above eq. (8.38) can be simplified form second order kinetics to the “pseudo”-first order kinetics: r= −

dcP = k0  cP dt

(8:39)

where k0 stands for reaction rate constant of “pseudo”-first order: k0 = kHO;P  cHO

(8:40)

By integrating the above eq. (8.40) in the interval from t0 to t the following equation is obtained:   cP;t = k0  t ) cP;t = cP;0  ek0 (8:41) − ln cP;t0 where cM;0 and cM;t are concentrations of organic pollutant during the treatment. The value of “pseudo”-first order reaction rate constant k0 can be determined graphically when t is plotted in the relationship to cP [22, 39]. As stated previously, HO• react with variety of organic compounds at rather high rates. Hence, in Table 8.9 the reaction rates with most common groups of organic pollutants are summarized [39].

Table 8.9: Reaction rate constants of HO• and common groups of organic compounds. Organic compounds

k/[dm3 mol−1 s−1]

Chlorinated alkenes Phenols Organic compounds with nitrogen Aromatics Ketones Alcohols Alkanes

109–1011 109–1010 108–1010 108–1010 109–1010 108–109 106–109

Example 8.5. Different water contaminants and natural water constituents compete for reacting with hydroxyl radicals, thus affecting the overall efficiency of advanced oxidation treatment. The application of the kinetic data for the hydroxyl radicals can be used to determine which of several competing reactions will predominate in the aqueous solution in the presence of more compounds [40]. Second-

References

273

order rate constants for reaction of hydroxyl radicals with different compounds in aqueous solutions can be found in the literature [41, 42]. For example, when three solutes are present in water; phenol (c(Ph) = 1×10–3 mol dm−3) as a target pollutant, hydrogen peroxide (c(H2O2) = 1×10–4 mol dm−3) and sulphate (c(SO42-) = 6×10–4 mol dm−3), they compete for OH radicals according to the following reactions with the corresponding reaction rate constants [40–42]: Ph + HO ! PhðHOÞ  kðPhÞ = 6:6x109 dm3 mol − 1 s − 1

H2 O2 + HO ! H2 O + HO2  kðH2 O2 Þ = 2:7x107 dm3 mol − 1 s − 1
 SO24 − + HO  + H + ! SO4−  + H2 O k SO4 2 − = 1:2x106 dm3 mol − 1 s − 1 The extent of reaction is proportional to the product of the reaction rate constant and the concentration of the solute:
′ kðPhÞ′ cðPhÞ : kðH2 O2 Þ′ cðH2 O2 Þ : k SO4 2 − cðSO4 2 − Þ = 70000 : 3 : 1 Accordingly, > 99.9 % of hydroxyl radicals reacting in the system would be effectively consumed in reaction with phenol, while with their loss in side reactions could be considered as negligible.

References [1]

Chaussade J-L, Mestrallet G. Water treatment handbook. Volume 1. 7th ed. France: Degrémont, Rueil-Malmaison, Lavoisier SAS, 1995. [2] Sundstrom DW, Klei HE. Wastewater treatment. Englewood Cliffs, NY, USA: Prentice-Hall, Inc., Prentice-Hall, 1979. [3] Kaštelan-Macan M, Petrović M. Analitika okoliša (in Croatian language). Zagreb, Croatia, Denona: HINUS and Faculty of Chemical Engineering and Technology, 2013. [4] Fifield FW, Haines PJ. Environmental analytical chemistry. 2nd ed. Oxford, UK: Blackwell Science Ltd, Blackwell Science, 2000. [5] Baker RW. Membrane technology and applications, 2nd ed. Sussex: John Wiley & Sons, Ltd, 2004. [6] Mulder M. Basic principles of membrane technology. 2nd ed. Dordrecht: Kluwer Academic Publisher, 1996. [7] Cui ZF, Muralidhara HS. Membrane technology – A practical guide to membrane technology and application in food and bioprocessing. Oxford: Elsevier, 2010. [8] Dolar D, Košutić K. Removal of pharmaceuticals by ultrafiltration (UF), nanofiltration (NF), and reverse osmosis (RO). In: Petrović M, Barcelo D, Perez S, editors. Comprehensive analytical chemistry, Vol. 62. Amsterdam: Elsevier, 2013: 319–44. [9] American Water Works Association Research Foundation. Water treatment membrane processes. New York: McGraw-Hill, 1996. [10] Subramani A, Jacangelo JG. Emerging desalination technologies for water treatment: A critical review. Water Res. 2015;75:164–87.

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[23] [24] [25] [26] [27]

[28] [29] [30]

[31] [32] [33]

8 Water and wastewater treatment engineering

Membranes Market by Type (Polymeric, Ceramics), Technology (RO, UF, MF, NF, Pervaporation, Gas Separation), Application (Water & Wastewater Treatment, Food & Beverage, Medical & Pharmaceutical, Industrial Gas Processing), Region - Global Forecast to 2021. http://marketsandmarkets.com. Accessed 2017 at: http://www.marketsandmarkets.com/Market-Reports/ membranes-market-1176.html. Koltuniewicz A, Drioli E. Membrane in clean technology. Theory and practice, vols 1–2. Weinheim: Wiley-VCH Verlag GmbH & Co. KGaA, 2008. Tchobanoglous G, FL B, Stensel HD. Wastewater engineering: treatment and reuse. New York: Metcalf & Eddy, Metcalf, Inc., 2003. Bitton G. Wastewater microbiology. New York: John Wiley & Sons, 2005. Casey TJ. Unit treatment processes in water and waste engineering. New York: John Wiley & Sons, 1996. Wang LK, Pereira NC, Hung Y-T. Biological treatment processes. New York: Humana Press, 2009. Gunder B. The membrane-coupled activated sludge process in municipal wastewater treatment. Lancaster: Technomic Publishing Co., Inc., 2001. Parsons S. Advanced oxidation processes for water and wastewater treatment. London, England: IWA Publishing, 2004. Litter MI, Candal RJ, Meichtry JM. Advanced oxidation technologies: sustainable solutions for environmental treatments. London, UK: CRC Press, Taylor and Francis, 2014. Gogate PR, Pandit AB. A review of imperative technologies for wastewater treatment I: oxidation technologies at ambient conditions. Adv Environ Res. 2004;8:501–51. Koprivanac N, Kusic H. Hazardous organic pollutants in colored wastewaters. New York: Nova Science Publishers, Inc., 2009. Beltran FJ. Ozone-UV radiation-hydrogen peroxide oxidation technologies. In: Tarr MA, editor. Chemical degradation methods for wastes and pollutants, environmental and industrial applications. New York, USA: Marcel Dekker, Inc., 2003: 1–77. Mantzavinos D, Psillakis E. Enhancement of biodegradability of industrial wastewaters by chemical oxidation pre-treatment. J Chem Technol Biotechnol. 2004;79:431–54. Andreozzi R, Vaprio V, Insola A, Marotta R. Advanced oxidation processes (AOP) for water purification and recovery. Catal Today. 1999;53:51–59. Fenton HJH. On a new reaction of tartaric acid. Chem News. 1876;33:190. Fenton HJH. Oxidation of tartaric acid in presence of iron. J Chem Soc, Trans. 1894;65: 899–910. Tarr MA. Fenton and modified Fenton methods for pollutant degradation. In: Tarr MA, editor. Chemical degradation methods for wastes and pollutants, environmental and industrial applications. New York, USA: Marcel Dekker, Inc., 2003: 165–200. Kušić H, Koprivanac N, Lončarić Božić A, Selanec I. Photo-assisted Fenton type processes for the degradation of phenol: a kinetic study. J Hazard Mater. 2006;B136:632–44. Kavitha V, Palanivelu K. The role of ferrous ion in Fenton and photo-Fenton processes for the degradation of phenol. Chemosphere. 2004;55:1235–43. Juretic Perisic D, Gilja V, Novak Stankov M, Katancic Z, Kusic H, Lavrencic Stangar U, et al. Removal of diclofenac from water by zeolite-assisted advanced oxidation processes. J Photochem Photobiol. 2016;321:238–47. Kusic H, Peternel I, Ukic S, Koprivanac N, Bolanca T, Papic S, et al. Modeling of iron activated persulfate oxidation treating reactive azo dye in water matrix. Chem Eng J. 2011;172:109–21. Legube B, Karpel Vel Leitner N. Catalytic ozonation: a promising advanced oxidation technology for water treatment. Catal Today. 1999;53:61–72. Vilhunen S, Sillanpaa M. Recent developments in photochemical and chemical AOPs in water treatment: a mini review. Rev Environ Sci Biotechnol. 2010;9:323–30.

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[34] Pichat P. Photocatalysis and water purification: from fundamentals to recent applications. Germany: Wiley, Weinheim, 2013. [35] Chong MN, Jin B, Chow CWK, Saint C. Recent developments in photocatalytic water treatment technology: a review. Water Res. 2010;44(10):2997–3027. [36] Pelaez M, Nolan NT, Pillai SC, Seery MK, Falaras P, Kontos AG, et al. A review on the visible light active titanium dioxide photocatalysts for environmental applications. Appl Catal B: Environ. 2012;125:331–49. [37] Schneider J, Matsuoka M, Takeuchi M, Zhang J, Horiuchi Y, Anpo M, et al. Understanding TiO2 photocatalysis: mechanisms and materials. Chem Rev. 2014;114:9919–86. [38] Legrini O, Oliveros E, Braun AM. Photochemical process for water treatment. Chem Rev. 1993;93(2):671–98. [39] Rodriguez M. Fenton and UV-VIS based advanced oxidation processes in wastewater treatment: Degradation, mineralization and biodegradability enhancement, PhD Thesis, University of Barcelona, 2003. [40] Lukeš P. Water treatment by pulsed streamer corona discharge, PhD Thesis, Published by Institute of Chemical Technology, Prague and Institute of Plasma Physics AS CR, 2001. [41] Buxton GV, Greenstock CL, Helman WP, Ross AB. Critical review of rate constants for reactions of hydrated electrons, hydrogen atoms and hydroxyl radicals (.OH/.O-) in aqueous solution. J Phys Chem Ref Data. 1988;17:513–886. [42] NIST Standard Reference Database 40, NDRL/NIST Solution Kinetics Database; National Institute of Standards and Technology, USA. Accessed at March 8, 2018: http://kinetics.nist. gov/solution/Detail?id=1982FIE/RAG2443-2449:7

Discussion, Questions and Exercises 1. 2. 3. 4.

5.

6.

7.

Explain the difference between the criteria and standards for water quality. Which parameters in the characterization of water are required to determine before re-using water or its discharge into the environment? What is the difference between the biological, physical and chemical characterization of the water? What analytical methods are used for the analysis of inorganic and organic traces contaminants and which requirements of that method must be satisfied and why? Concentration of chloride ions in feed, concentrate and permeate streams are 1000, 3800, and 200 mg L−1, respectively. Designed recovery rate for the RO unit is 75 %. According to the concentrations of chloride ions calculate actual recovery rate. (Solution: Y = 78 %) Concentration of solute in feed water is 500 mg L−1 and is treated with nanofiltration membrane. Rejection of this solute with NF membrane is 90 %. Calculate concentration of solute in permeate. (Solution: γp = 50 mg L−1) RO unit contains 3 membrane modules. Feed flow rate is 1000 m3 d−1. Calculate permeate and retentate flow rate for each membrane module if recovery for one module is 15 %. Also calculate overall recovery of this process. (Solution: Qp,1 = 150.0 m3 d−1; Qr,1 = 850.0 m3 d−1; Qp,2 = 127.5 m3 d−1; Qr,2 = 722.5 m3 d−1; Qp,3 = 108.4 m3 d−1; Qr,3 = 614.1 m3 d−1, and Y = 38.6 %)

276

8.

8 Water and wastewater treatment engineering

Two-step process is presented in the diagram below together with feed flux and concentrations of DOC and Ca. In 1st and 2nd stage 7 and 3 vessels were used, respectively. In each vessel were 7 NF modules. A recovery for modules is given in Table 8.4 in Example 8.2.

Qf = 1540 m3 d-1 γf,Doc = 7 mg L-1 γf.Ca = 140 mg L-1

2. stage

1. stage

Qr2

Qr1 γr1,Doc γr1,Ca

Qp1 γp1,Doc γp1,Ca

γr2,Doc γr2,Ca Qp2 γp2,Doc γp2,Ca

Qr γr,Doc γr,Ca

Solution:

2. stage

1. stage Qf = 1540 m3 d-1

Qr1 =518 m3 d-1

γf,Doc = 7 mg L-1 γf.Ca = 140 mg L-1

γr1,Doc=19.7 mg L-1 γr1,Ca=400 mg L-1 Qp1=1022 m3 d-1 γp1,Doc=0.56 mg L-1 γp1,Ca=11.3 mg L-1

Qr2=195 m3 d-1

Qp2=323 m3 d-1

γr2,Doc=49.7 mg L-1 γr2,Ca=1009 mg L-1

γp2,Doc=1.51 mg L-1 γp2,Ca=30.5 mg L-1 Qp=1345 m3 d-1 γr,Doc=0.79 mg L-1 γr,Ca=15.9 mg L-1

9. 10. 11. 12. 13. 14. 15. 16.

What is the relationship between the BOD and COD values in wastewater? What are the advantages of membrane bioreactor over conventional processes for wastewater treatment? What is activated sludge? How to calculate the parameters μmax and Ks? Describe the main advantages and constrains of AOPs in water treatment. What is the main oxidative specie in all AOPs and how it may be generated? What is the operating pH range in Fenton process? What would happen with ferrous and ferric iron at basic conditions? Describe the underlying phenomena of photocatalytic AOPs using semiconductors.

Ivica Kisić, Željka Zgorelec and Aleksandra Percin

9 Soil treatment engineering Abstract: Soil is loose skin of the Earth, located between the lithosphere and atmosphere, which originated from parent material under the influence of pedogenetic processes. As a conditionally renewable natural resource, soil has a decisive influence on sustainable development of global economy, especially on sustainable agriculture and environmental protection. In recent decades, a growing interest prevails for nonproduction soil functions, primarily those relating to environmental protection. It especially refers to protection of natural resources whose quality depends directly on soil and soil management. Soil contamination is one of the most dangerous forms of soil degradation with the consequences that are reflected in virtually the entire biosphere, primarily at heterotrophic organisms, and also at mankind as a food consumer. Contamination is correlated with the degree of industrialization and intensity of agrochemical usage. It is typically caused by industrial activity, agricultural chemicals or improper disposal of waste. The negative effects caused by pollution are undeniable: reduced agricultural productivity, polluted water sources and raw materials for food are only a few of the effects of soil degradation, while almost all human diseases (excluding AIDS) may be partly related to the transport of contaminants, in the food chain or the air, to the final recipients – people, plants and animals. The remediation of contaminated soil is a relatively new scientific field which is strongly developing in the last 30 years and becoming a more important subject. In order to achieve quality remediation of contaminated soil it is very important to conduct an inventory as accurately as possible, that is, to determine the current state of soil contamination. Keywords: soil science, soil contaminants, remediation technologies

9.1 Introduction While practical knowledge and empirically obtained insights about the soil have their origin in the most ancient history, soil science has developed as an independent science in the mid-nineteenth century. Soil was mentioned in the oldest scientific book Papyrus Ebers from the sixteenth century BC, and also Greek and Roman writers have been working on the issue of soil fertility and classification. Ancient History and the Middle Ages were centuries of empiricism. The entire knowledge on soil from that time remains

This article has previously been published in the journal Physical Sciences Reviews. Please cite as: Kisic, I., Zgorelec, Z., Percin, A. Soil Treatment Engineering. Physical Sciences Reviews [Online] 2017, 2 (11). DOI: 10.1515/psr-2016-0124 https://doi.org/10.1515/9783110468038-009

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9 Soil treatment engineering

based on the experience, and that knowledge was collected mainly for agricultural purposes. The progress of chemistry has accelerated the development of knowledge on the soil. In the second half of the eighteenth century, when the chemistry was so advanced, knowledge of the major chemical principles and analytical procedures has enabled the determination of the composition of living and dead inorganic and organic substances. Biochemistry has developed and the first studies of the soil begun. At first, the knowledge of the soil was obtained as a part of the geologic system – as geochemistry or agrogeology, chemistry or general crop science, and later as a collection of different sciences that can be applied in agriculture and forestry. The first scientific work about the soil, Bodenkunde – oder die Lehre vom Boden by German agrochemist Carl Sprengel (1787–1859), was published in 1837. Soil science had soil fertility in its focus for a long time, as an expression of indisputably the most important productive role of soil in agriculture and forestry. Only recently, more attention is given to the other roles of soil. Based on all the above reasons, all nations classify soil as the most important national natural resource, that is, as a member of the so-called environmental triad: AIR – SOIL – WATER.

9.2 Basics of soil science When speaking about the soil it is most important to point out that we obtain more than 95% of food and raw materials for food from the soil. At the same time, a favorable fertile soil for this purpose is a very limited resource (Figure 9.1).

Frozen soils 6% Humid soils 10%

Soils without limitations 11%

Dry soils 28%

Shallow soils 22%

Acidic and salty soils 23%

Figure 9.1: The percentage share of the soil surface with different restrictions for agricultural use of the world’s total soil area [1]. (Adopted from FAO)

There are several definitions of the soil. The simplest definition is: soil is the surface layer of the Earth’s crust altered by the combined influence of climate, air, water, plants

9.2 Basics of soil science

279

and animals. From the ecological point of view, soil is the layer of the Earth’s crust that provides optimum conditions for plant growth. Based on the above-mentioned definitions, we can say that soil is loose skin of the Earth, located between the lithosphere and atmosphere, which arose from parent material under the influence of factors of pedogenesis and pedogenesis process (Figure 9.2). Soil is a natural product created by complex processes, first by fragmentation and decomposition of rocks, i.e. primary minerals of parent material, and by synthesis – the formation of new, secondary minerals. The resulting mass can hold water, which allows colonization, primarily by bacteria, fungi, algae and lichen, and finally by higher plants. The names of soil in different languages are: počv (Bulgarian), tlo (Bosnian and Croatian), púda (Czech), Έδαφος (Greek), jord (Danish, Norwegian and Finnish), Boden (German), soil (English), grundo (Esperanto), suelo (Spanish), sol (French), talaj (Hungarian), suolo (Italian), počva (Russian and Macedonian), bodem (Dutch), gleba (Polish and Belarusian), solo (Portuguese), sol (Romanian), poda (Slovak), prst (Slovenian), zemljište (Serbian), toprak (Turkish) and grunt (Ukrainian).

Figure 9.2: Soil [1]. (Photo by: Z. Zgorelec, 2007).

The biggest difference between soil and rock is in the content of organic matter. Agricultural soil contains 0.5–5% of organic matter, and peat soil up to 50% of organic matter. Although its content in agricultural soils is relatively small, the organic matter brings and maintains life in the soil. Without organic matter, soil would no longer be soil but a lively rock from which the soil was created. In this case, soil would lose its primary role, which is the supply of plants with water, air and nutrients [2]. It is necessary to clearly distinguish between the two terms that are frequently replaced

280

9 Soil treatment engineering

and cause confusion – soil and land. The difference is obvious. Soil was already described as a natural product created by processes of soil formation (pedogenesis), and the term land refers to the land area (Figure 9.3). Land is a broader concept – it’s a land (terrestrial) surface and bio-productive system that includes soil, vegetation, other biota, and the ecological and hydrological processes that occur in the entire system. We have already mentioned the names of soil in the major European languages, and the names of the land are in French – terre, English – land (landscape), Russian – zemlja, Italian – terreno, Dutch – landen, Polish – kraina or parcela, and German – Erde. And finally, a few words on the concept of pedology. Although it is in many languages a deep-rooted word (pedology), it is the concept that outsiders often replace with the concept of pedology as a science of physical and mental development of children. Therefore, the term soil science is increasingly used in recent years.

Figure 9.3: Land [1]. (Photo by: I. Kisic, 2011).

9.3 Soil formation 9.3.1 Factors and processes of soil formation There are four main factors of pedogenesis: lithosphere (parent material), atmosphere, hydrosphere and biosphere. Lithosphere has a passive role, and the other

9.3 Soil formation

281

three spheres actively participate in development processes of pedosphere. The atmosphere acts in particular via precipitation, heat, wind and gas; hydrosphere acts via movement and strength of water masses; the biosphere acts via most diverse organisms, primarily with flora, fauna and human activity. The formation of soil is a long process which lasts for thousands of years, and in some substrates such as limestone it lasts for hundreds of thousands, or even a million years. To form one centimeter layer of red soil (terra rossa) as the most valuable type of soil on the limestone of the Mediterranean, it requires a flow of 8,000–10,000 years, therefore for 1 m depth it takes 800,000–1,000,000 years. A man can destroy it by improper management in several dozen years or permanently convert it in a few days. We distinguish five basic groups of pedogenetic processes: depletion of lithosphere; formation of organic matter; degradation (decomposition) of organic matter; displacement of components (translocation) and the new formation (neogenesis). Weathering of parent materials is changing the physical and chemical properties of the lithosphere. The compact masses of rock disintegrate and are then made from the same mineral compounds and partly of new mineral compounds. Surface mass significantly increases, and their atoms and atomic groups are more mobile than they were in compact rocks of the lithosphere. Processes of formation of organic matter enrich the mineral erosion with the living organic matter that becomes an important factor in the dynamics and development of soil. Processes of decomposition (rotting, decay) of organic matter result in many chemically and physiologically active compounds that enter in reactions with disintegrated minerals. Processes of transfer can change the position of the mass, or soil particles, on the surface of pedosphere or in its interior. Surface displacement is the most important factor in the development of the external morphology of pedosphere. The most diverse morphological forms are developed according to the forces participating in the surface displacement of pedosphere mass (rain, floods, river, sea, glaciers, wind, etc.). Processes of the new formation of the rock weathering products and the products of degradation of organic matter created new inorganic and organic complexes, of which the most important and most active are the colloidal components of soil – the secondary minerals or clay minerals and humus. These components significantly alter the features of erosion.

9.3.2 Basic soil characteristics Soil formation was briefly summarized in the previous section. The basic physical, chemical and biological properties of soil and fertility, as a result of these qualities, are presented in this section. According to its physical characteristics, soil is a threepart system that has a solid, liquid and gaseous component. The ratio of individual

282

9 Soil treatment engineering

components is a dynamic value (especially the ratio of liquid and gaseous components), dependent on the mechanical composition of soil, climate, current weather conditions, and the season, as well as on all other external factors. The solid component consists of mineral and organic parts. Mineral part originates from parent material, and the organic is more or less a humified organic matter. The liquid component of soil is water, more specifically, an aqueous solution of soil. The most important physical parameter of the soil is the granulometric composition of the soil. The solid component of the soil is by nature a polydisperse system that consists of particles of different dimensions, from the ions, molecules and colloids that are invisible to the naked eye, to the particles of stone. Each particle, that can’t continue to break into pieces by weak mechanical forces (or peptization), is called a mechanical or granulometric element. Mechanical components in the soil are rarely found separately and they are connected to the larger particles – structural aggregates. The term mechanical composition or texture means the content of individual fractions in the soil in weight percent (Table 9.1). As the lower and upper limits for the classification of mechanical fractions according to the particle size are conventional values, different classification is applied in the world. Textural classes are determined by, among other things, the Atterberg triangle that has data on the percentage of silt, sand and clay graphically applied on every side of it, and the intersection can show a texture mark, as shown in Figure 9.4. According to their characteristics, all classes can be divided into three basic groups, or types of soil: sand, loam and clay soils. It is widely accepted that the clay soils are labeled as heavy soils, and sandy soils as light soils. The increased soil fragmentation (dispersion) in the same conditions increases the holding power of water, adsorption capacity, the amount of related nutrients, swelling, stickiness and plasticity, and decreases the permeability of water – internal natural drainage. Shortly, the chemical properties of the soil are improved and the physical properties deteriorate.

Table 9.1: International classification of granulometric composition [3]. Soil with a diameter greater than 2 mm

Soil with a diameter less than 2 mm

Rock Gravel

Coarse sand Fine sand Dust/powder Clay

More than 20 mm 20–2.0 mm

Stony soils I. Absolutely stony soils: more than 90% of the stone II. Very stony soils: 70–90% of the stone III. Stony soils: 50–70% of the stone

2.0–0.2 mm 0.2–0.02 mm 0.02–0.002 mm All,AxesLabel->{“t/h”,“cA/mol/L”}]

dcA = −k
cA

Zt dt 0

ln cA − ln cA, 0 = − k
t ln cA = − k
t + ln cA, 0 cA = cA,

0


e

6

− k
t

5

cA (mol/L)

4 3 2 1 0 0

20

40

60 80 t (h) Figure (b): Graphical solution of mathematical model

100

Table 10.1: Comparison between analytical and numerical solution of mathematical model for pollutant A concentration profile. t/h cA (analytical)/mol/L cA (numerical)/mol/L

0 5 5

5

10

1.072 0.229 1.072 0.230

20 0.011 0.011

50

80

–6

–11

1.025 · 10 1.029 · 10–6

100

9.953 · 10 2.102 · 10–13 –11 9.725 · 10 2.939 · 10–13

The next step is model interpretation or verification of model solution. It is necessary to evaluate if the model behaves correctly and if the obtained answer is expected. If the answer on one of these two questions is no, a stepback is necessary in order to perform some corrections of the model. If the answers are yes, the final step of mathematical modeling is validation. There are various ways to validate a model and they depend on process system, purpose of modelling and ability to collect independent data about the system. Model validation can be performed by: – Verifying experimentally the assumptions for the simplification, – Comparing the model behavior with the process behavior,

10.3 Basic rules in mathematical modeling

– – –

329

Developing analytical models for simplified cases and comparing their behavior, Comparing with other models using a common problem and Comparing the model directly with process data.

A poor approach is to validate a model based on the data that were used for model development and model parameter estimation. Additionally, there are some model properties that enable its validation: – Accuracy – model is accurate if the model response is satisfactory close to the response of real system, – Realism in system description – model is based on assumptions about mechanisms that are close to those in real system, – Precision – a unique solution (i. e. a result of model simulation is only one x–y dependence not a bundle of curves), – Robust – model is not sensitive to “noise” that is present in input data and, – Generality – possibility to apply model on wide range of problems. Table 10.2: Comparison of analytical and numerical solution of mathematical model with experimental data for pollutant A concentration profile. t/h

0

cA (analytical)/mol/L cA (numerical)/mol/ cA (experimental)/mol/L

5 5 5

5

10

1.072 0.229 1.072 0.230 1 0.2

20 0.011 0.011 0.01

50

80

–6

–11

1.025 · 10 1.029 · 10–6 0

9.953 · 10 2.102 · 10–13 –11 9.725 · 10 2.939 · 10–13 0 0

figure1 = Plot[kcA[t],{t,0,tf},PlotRange->All,AxesLabel->{“t/h”,“cA/mol/L”}]; data = {{0,5},{5,1},{10,0.2},{20,0.01},{50,0},{80,0},{100,0}}; figure2 = ListPlot[data]; Show[{figure1,figure2}] 6 5

cA (mol/L)

4 3 2 1 0 0

20

40

100

60 80 100 t (h) Figure (c): Graphical comparison of solution of mathematical model and experimental data.

330

10 Modeling of environmental processes

Once the model is developed and validated, it can be used for many different purposes: optimization, process control, process design, finding flaws in the process, etc. By applying mathematical models, analysis and measurements that are timeconsuming or even impossible to perform in reality become possible and solvable in a short period of time. The number of possibilities is endless. Model application: (b) Component A half-life cA = cA,0
e − k
t − 0.308
t

0.5
cA,0 = cA,0
e ln0.5 = − 0.308
t t = 2.250 h

(c) Time to achieve 95% degradation at T = 17 °C Ea

50000

k = A
e − R
T = 2.5
108
e − 8.314
290.15 = 0.249 1=h cA = cA,0
e − k
t 0.05
cA,0 = cA,0
e − 0.249
t ln0.05 = − 0.249
t t = 12.031 h

Example 10.2. Pollutant A is being removed from the wastewater of pharmaceutical industry in batch reactor that has volume of V = 200 L. Degradation of the pollutant A can be described with second-order kinetics with reaction rate constant k = 0.005 mol/L·h. Initial concentration of the pollutant A is cA,0 = 5 mol/L. a. Compare an analytical and numerical solution for the concentration change of the pollutant A during the time period of 100 h at specific time point listed in table. b. Define the time necessary to achieve 95% degradation of the pollutant A. c. Define the time necessary to achieve 95% degradation of the pollutant A if process would be performed at continuous stirred tank reactor that has volume of V = 100 L at constant flow rate of q = 30 L/h. d. Wastewater treatment system operates under constant temperature conditions (T = 20 °C). In case of temperature control failure, reverse reaction mechanics occurs (2A⇄B). Calculate the concentration of the pollutant A if the temperature regulation failure occurs at the tenth hour of the degradation and it lasts for 3 h. In the moment of the failure, the concentration of the pollutant A in reactor is cA = 4 mol/L and the concentration of the component B is cB = 1 mol/L. Reaction rate constant of reverse reaction is k2 = 0.001 mol/L·h. (a) Change of concentration of reactant A in time in batch reactor Process system: – batch reactor – constant volume, V = const. – constant density, Δ0= Δ – constant temperature, T = const.

Figure (a): Batch reactor. Purpose/goal of modeling: To predict change of concentration of reactant A in time Defining the mechanisms: Chemical reaction (A ↔ B), second order (rA = k·cA2)

331

10.3 Basic rules in mathematical modeling

Information’s about the process system: cA,0 = 5 mol/L V = 200 L T = 20 °C Model assumptions: – ideal mixing – V = const.; T = const. Masass balance: dcA dt

= − k
cA2

Solving the model: (a) Analytical solution dcA dt

= −k


dcA c2 A

= − k
dt

ZcA

dcA = −k
cA2

cA,0

− 1 cA



1 cA

=

cA2

−

1 cA,0

1 cA,0



Zt

(b) Numerical solution k = 0.005; cA0 = 5; tf = 100; model = NDSolve[{cA’[t] = = -k×cA2[t],cA[0] = = 5},cA,{t,0,tf}] kcA[t_]: = cA[t]/.model

dt 0

= −k
t

Plot[kcA[t],{t,0,tf},PlotRange->All,AxesLabel->{“t/h”,“cA/mol/L”}]

+k
t

Table 10.3: Comparison between analytical and numerical solution of mathematical model for pollutant A concentration profile. t/h

0

5

10

20

50

cA (analytical)/mol/L cA (numerical)/mol/L

5 5

4.444 4.444

4.000 4.000

3.333 3.333

2.222 2.222

Application: (b) Time necessary to achieve 95% degradation of the pollutant A 1 cA

=

1 cA,0

1 0.1
cA,0

=

+k
t 1 cA,0

+ 0.005
t

(c) Time necessary to achieve 95% degradation of the pollutant A in continuous stirred tank reactor d dt ðV
cA Þ = q
cA,0 − q
cA − V
rA dc V
dtA = q
ðcA,0 − cA Þ − V
k
cA2 dcA q 2 dt = V
ðcA,0 − cA Þ − V
k
cA dcA dt

=

q V


ðcA,0 − cA Þ − k
cA2

80

100

1.667 1.428 1.667 1.428

332

10 Modeling of environmental processes

ZcA cA,0

q V

dcA =
ðcA,0 − cA Þ − k
cA2

Zt dt 0

t = 0.192 h (d) Change of concentration of reactant A in batch reactor after reaction mechanism change dcA dt dcB dt

= − 2
k
cA2 + k2
cB = 2
k
cA2 − k2
cB

1 dcA αA dt dcA dt =

=

1 dcB αB dt ↔cB

= 0.5
ðcA,0 − cA Þ + cB,0

− 2
k
cA2 + k2
0.5
ðcA,0 − cA Þ + cB,0

cA = 3.574 mol=L Example 10.3. Exothermic reaction of the burning the waste (ρ = 1200 kg/m3) containing toluene is taking place in tubular reactor with active volume of V = 1500 L. Reaction can be described by first-order kinetics. Reactor has diameter of R = 0.4 m, flow rate through reactor is q = 200 L/min and concentration of the toluene at the inflow is ci = 10 mol/L. Temperature at the inflow is Ti = 40 °C, and the temperature in heat exchanger To = 130 °C. Heat transfer coefficient is kQ = 5.2 W/m2⋅K and specific heat capacity cP = 4.5 kJ/kg⋅K. Reaction enthalpy is (–ΔHA) = 80 kJ/mol and parameters of the Arrhenius model are A = 3.6 ⋅ 103 1/s, Ea = 42 kJ/mol. a. Set the balances for the mass and heat change over the time. b. Set the balances for the mass and heat change in dimensionless form and calculate the specific dimensionless numbers. c. Define the distribution of conversion and temperature. d. Calculate the conversion, concentration of the toluene and the temperature at the reactor outflow. (a) Balances for the mass and heat change over the time in a tubular reactor mass inflow: F1 = S
v
cðt, x Þ mass outflow: F2 = S
v
cðt, x + Δx Þ reaction: FR = Δx
S
r ðcÞ mass accumulation: m = S
Δx
cðt, x Þ mass change over time: Δm Δt = F1 − F2 − FR Figure (d): Tubular reactor. Δ Δt ðS
Δx
cðt, x ÞÞ = S
v
cðt, x Þ − S
v
cðt, x + Δx Þ − Δx cðt, x + Δx Þ − cðt, x Þ Δ − r ðcÞ Δx Δt cðt, x Þ = − v
  Δ  cðt, x + Δx Þ − cðt, x Þ − r ðcÞ lim Δt cðt, x Þ = − v
lim Δx Δt!0 Δx!0 ∂ ∂t cðt, x Þ =

ðt, x Þ − v
∂c∂x − r ðcÞ

Initial conditions:

cðt = 0, x Þ = c0 ð x Þ

Boundary conditions:

cðt, x = 0Þ = ci ðt Þ

heat inflow:

F1 = S
v
ρ
cp
T ðt, x Þ

heat outflow:

F2 = S
v
ρ
cp
T ðt, x + Δx Þ


S
r ðcÞ

333

10.3 Basic rules in mathematical modeling

heat transfer through heat exchanger wall: reaction heat:

  F3 + F4 = 2
R
π
Δx
kQ
T ðt, x Þ − Tp QR = ð − ΔHA Þ
S
Δx
r ðcÞ

heat accumulation:

Q = S
Δx
ρ
cp
T ðt, x Þ ΔQ Δt

heat change over time:

= F1 − F2 + QR − ðF3 + F4 Þ

Δ Δt ðS


Δx
ρ
cP
T ðt, x ÞÞ = S
v
ρ
cP
T ðt, x Þ − S
v
ρ
cP
T ðt, x + Δx Þ + ð − ΔHA Þ
S
Δx
r ðcÞ   − 2
R
π
Δx
kQ
T ðt, x Þ − Tp ð − ΔHA Þ
rðcÞ 2
kQ
ðT ðt, xÞ − Tp Þ T ðt, x + Δx Þ − T ðt, x Þ Δ + − Δt T ðt, x Þ = − v
ρ
cp ρ
cp
R Δx    ð − ΔHA Þ
rðcÞ 2
kQ
ðT ðt, x Þ − Tp Þ Δ lim Δt T ðt, x ÞÞ = − v
lim T ðt, x + ΔxΔxÞ − T ðt, xÞ + − ρ
cp ρ
cp
R

Δt!0

Δx!0

∂ ∂t T ðt, x Þ =

ðt, x Þ − v
∂T∂x +

ð − ΔHA Þ
rðcÞ ρ
cp

−

2
kQ
ðT ðt, x Þ − Tp Þ ρ
cp
R

Initial conditions:

T ðt = 0, x Þ = T0 ð x Þ

Boundary conditions:

T ðt, x = 0Þ = Ti ðt Þ

Steady-state balances:

− R
T
c = 0 − v
∂c ∂x − A
e

− v
∂T ∂x +

ð − ΔHA Þ ρ
cp

Ea

Ea


A
e − R
T
c −

2
kQ
ðT − Tp Þ ρ
cp
R

=0

(a) Balances for the mass and heat change over the time in a tubular reactor in dimensionless form Ea

− R
T
c = 0 mass change steady-state concentration: − v
∂c ∂x − A
e

relative concentration:

y=

relative distance:  

ξ=

−v
−

∂y ∂ξ

ci
∂ cc  i L
∂ x L

Ea

− A
e − R
T
ci
e  

− Da
e

−ε 1 −1 θ

cðt, x Þ ci x L 

− Ea R
TR



1 −1 T TR

2

−v
−

∂θ ∂ξ

TR L




 

+ β
Da
e

ð − ΔHA Þ
ci ρ
cp



−ε 1 −1 θ

Ea

A
e − R
T


Arrhenius number: Ea ε = R
T 0



1 −1 T − Ea R
TR T R e


cc −



i

2
kQ
TR R
ρ
cp






T TR

−

TP TR

 =0


y − St
ðθ − θP Þ = 0

Dimensionless reaction temperature: β=

θ=

i



+

relative temperature:

t t L=v = τ 0 T ðt, x Þ TR


y=0

− Ea e R
T0

Ti
∂ T  TR
∂ x L

τ=


cc = 0

Damkohler number: Da = τ
A


relative time:

ð − ΔHA Þ
ci

Stanton number: St =

ρ
cP
TR

2
kQ
L R
ρ
cP
v

Balances expressed with the conversion:   −ε

∂x ∂τ

=−

∂x ∂ξ

+ Da
e

∂θ ∂τ

=−

∂θ ∂ξ

+ β
Da
e

1 θ−1




ð1 − x Þ = 0 

−ε 1 −1 θ


ð1 − x Þ − St
ðθ − 1Þ = 0

Initial conditions: x ðτ = 0, ξ Þ = x0 ðξ Þ θðτ = 0, ξ Þ = θ0 ðξ Þ

Boundary conditions: x ðτ, ξ = 0Þ = 0 θðτ, ξ = 0Þ = θi ðτ Þ

334

10 Modeling of environmental processes

Calculation of dimensionless numbers using Wolfram Mathematica 10.0. V = 1500×10–3; q = 200×10–3/60;

(*reactor length*) L = N[V/(r2×Pi)];

r = 0.4;

(*average residence time*)

ci = 10*103; R = 8.314;

τ = V/q; (*Damkohler number*)

Ti = 40 + 273.15;

Da = τ×k0×Exp[–(Ea/(R×To))];

To = 130 + 273.15; kQ = 5.2;

(*dimensionless reaction temperature*) β = (ΔH×ci)/(ρ×cp×To);

ρ = 1200;

(*Arrhenius number*)

cp = 4.5×103; k0 = 3.6×103;

ϵ = Ea/(R×To); (*Stantons number*)

Ea = 45×103;

St = (kQ×2×r×Pi×L)/(q×cp×ρ);

ΔH = 80×103; Print[“reactor length = ”,L] Print[“average residence time = ”,τ] Print[“Damkohler number = ”,Da] Print[“dimensionless reaction temperature = ”,β] Print[“Arrhenius number = ”,ϵ] Print[“Stantions number = ”,St] reactor length = 2.98416 average residence time = 450 Damkohler number = 2.39234 dimensionless reaction temperature = 0.367476 Arrhenius number = 13.4257 Stantions number = 0.00216667 (c) Distribution of conversion and temperature over the time and reactor length model = NDSolve[{x’[ξ] = = Da*Exp[–ϵ×(1/θ[ξ]–1)]×(1-x[ξ]), θ’[ξ] = = -St*(θ[ξ]–1)+β×Da*Exp[–ϵ×(1/θ[ξ]–1)]×(1-x[ξ]), x[0] = = 0, θ[0] = = Ti/To}, {x,θ},{ξ,0,1}] kx[ξ_]: = x[ξ]/.model kθ[ξ_]: = θ[ξ]/.model

1.0

Plot[{kx[ξ],kθ[ξ]},{ξ,0,1},PlotRange-> All,PlotStyle-> {RGBColor[1,0,0],RGBColor[0,0,1]}]

0.8

X, θ

0.6 0.4 0.2 0.0

0.0

0.2

0.4

0.6

0.8

1.0

ζ (−)

Figure (e): Distribution of conversion and temperature

10.4 Balance equations – Solving mathematical models

335

(d) Calculation of the conversion, concentration of the toluene and the temperature at the reactor outflow. xoutflow = kx[1]; coutflow = ci×(1–kx[1])/1000; Toutflow = kθ[1]×To; Print[“conversion at the reactor outflow = ”,xoutflow] Print[“concentration at the reactor outflow = ”,coutflow] Print[“temperature at the reactor outflow = ”,Toutflow] conversion at the reactor outflow = {0.443806} concentration at the reactor outflow = {5.56194} temperature at the reactor outflow = {379.048}

10.4 Balance equations – Solving mathematical models As mentioned, universal tool for modeling are equations which are obtained by the balances for mass, energy or impulse that entered and exited the observed system in differential time and volume and generation and consumption within the observed system (Figure 10.8). They can be either differential or algebraic equations or in matrix-vector form. When talking about mathematical modeling of processes, differential equations are mostly used because algebraic equations are just not sufficient enough to describe all connections between inlet and outlet variable and all that is going on in the system. What type of equation will be used depends on (Figure 10.8): – dependent variables and their dependence on spatial position (lumped models or distributed models), – time dependence (stationary or dynamic), – purpose of modeling and – on how complex the process is.

Variable dependence on spatial position

Type of equations

Processes with lumped parametes

Processes with distributed parametes

Stationary

Dynamic

Stationary

Dynamic

Parabolic or hyperbolic partial differential equations

Elliptic partial differential equations

Differential or linear algebraic equations

Nonlinear algebraic equations

Figure 10.8: Types of equations used for describing mathematical models of the process.

336

10 Modeling of environmental processes

In order to solve different types of equations, there are again different mathematical/numerical approaches. In this chapter, only list of methods for solving them with short explanation together with some examples will be given due to many examples available. To solve linear equations, methods can be divided into: – direct – that provide exact solution – Gauss elimination (solving principle is demonstrated in Example 10.4) – Equations are written in matrix form and the method is based on a sequence of operations performed on the corresponding matrix of coefficients. General form: 0 1 0 1 0 1 x1 b1 a11 a12 a13 ... a1n B a21 a22 a23 ... a2n C B x2 C B b2 C B C B C B C B a31 a32 a33 ... a C
B x3 C = B b3 C 3n C B B C B C @ ... ... ... ... ... A @ ... A @ ... A an1 an2 an3 ... ann xn bn –

–

Gauss–Jordan method – Elements of transformations in Gauss elimination are expend until a matrix is convert into reduced row echelon form iterative/indirect – that start with assumption of solution and then compute iteratively a sequence of solutions that get closer and closer to the final solution – Gauss–Seidle method or Liebmann method or the method of successive displacement – In each iteration, a possible solution to the system with a particular error is obtained. Method is then repeated again until the solution is more accurate and error smaller. If the system does not converge and with every next step error is growing, the system cannot be solved by this method – Jacobi method – is an algorithm for determining the solutions of a diagonally dominant system of linear equations. Each diagonal element is solved for, and an approximate value is plugged in. The process is then iterated until it converges.

Example 10.4. Degradation of chemical contamination of component A to component C is three steps reaction performed in batch reactor and it follows the mechanism: A ⇄ B ð1Þ B ! C ð2Þ C ! B ð3Þ All reactions follow first-order kinetics (r = k·c) where reaction rates are: kA↔B = 5 mol/L, kB↔A = 7 mol/L, kB↔C = 3 mol/L and kC↔B = 2 mol/L. If, after 5 h, accumulations of components A, B and C are:

10.4 Balance equations – Solving mathematical models

dcA dt dcB dt dcC dt

337

= 18 mol=L
h = − 28 mol=L
h = 10 mol=L
h

define mathematical model of the process and calculate numerical concentration off all components in that moment using Gauss elimination method.

Process system: – Batch reactor – first-order reaction A⇄B ð1Þ B!C ð2Þ C!B ð3Þ

Figure (a): Batch reactor. Purpose/goal of modeling: To calculate numerical concentration of components A, B and C 5 h after the reaction started. Defining the mechanisms: Chemical reactions (A ⇄ B, B↔C and C↔B), first order kinetics (r = k·c) Information’s about the process system: kA↔B = 5 mol/L, kB↔A = 7 mol/L, kB↔C = 3 mol/L and kC↔B = 2 mol/L t = 5 h dcA dt dcB dt dcC dt

= 18 mol=L
h = − 28 mol=L
h = 10 mol=L
h

Model assumptions: – ideal mixing – V = const.; T = const.; Δ = const.

Mass balances: dcA dt dcB dt dcC dt

= − kA!B
cA + kB!A
cB = kA!B
cA − kB!A
cB − kB!C
cB + kC!B
cC = − kC!B
cC

Gauss elimination method: dcA dt dcB dt

= − kA!B
cA + kB!A
cB = − 5
cA + 7
cB = kA!B
cA − kB!A
cB − kB!C
cB + kC!B
cC = 5
cA − 7
cB − 3
cB + 2
cC = 5
cA − 10
cB + 2
cC

dcC dt

= kB!C
cB − kC!B
cC = 3
cB − 2
cC

Equation 1: − 5
cA + 7
cB + 0
cC = 18 Equation 2: 5
cA − 10
cB + 2
cC = − 28 Equation 3: 0
cA + 3
cB − 2
cC = 10 1 0 10 1 0 0 −5 7 18 −5 7 0 cA C B CB C B B @ 5 − 10 2 A @ cB A = @− 28 A ) @ 5 − 10 0

3 −2

cc

10

0

0

18

3 −2

10

1

C 2 − 28 A

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10 Modeling of environmental processes

Elements of the second row reduce by the values of the first. 1 0 − 5 7 0 18 C B @ 0 − 3 2 − 10 A 0

3 −2

10

Elements of the third row reduce by the values of the second. 1 0 − 5 7 0 18 C B @ 0 − 3 2 − 10 A 0

0

0

0

Elements of the first row divide by −5 and the second row by −3. 10 1 0 0 1 0 1 cA 1 − 1.4 0 1 − 1.4 0 − 3.6 3.6 CB C B B C B C 1 − 0.67 A @ cB A = @ 3.33 A 1 − 0.67 3.33 A ) @ 0 @0 0

0

0

0

0

0

0

cC

0

Written in algebraic form: cC = 0 mol/L cB = 3.33 mol/L cA = −3.6 + 1.4·cB = −3.6 + 4.66 = 1.06 mol/L

For solving non-linear equations mostly used methods (all iterative) are: – iterative/indirect – Jacobi non-linear iteration – Wegstein method – Newton–Raphson method or Newton’s method – Regula–Falsi method or false position Method For solving differential equations mostly used methods are: – Analytical methods – n-order differential equations that have n constants and n boundary conditions are solved simply by solving mathematical equations. Analytical solution is the exact solution of differential equation and it satisfies differential equation and boundary conditions. – Numerical methods – Taylor meth – od is based on the Taylor series that is a representation of a function as an infinite sum of terms that are calculated form the values of the function’s derivatives at a single point. Simple differential equation dydtðtÞ = f ðt, yðtÞÞ, yð0Þ = y0 can be approximated with Taylor series as yðt + ΔtÞ = yðtÞ + Δt
y′ðtÞ + 21
Δt2
y′′ðtÞ + ... + n!1
Δtn
yðnÞ ðτÞ – Euler method is based on the approximation of the function with the first component of the Taylor series (solving principle is demonstrated in Example 10.5) – Runge method (solving principle is demonstrated in Example 10.5)

10.4 Balance equations – Solving mathematical models

–

339

Runge–Kutta method also based on the Taylor series but more suitable for the solving of the differential equations than Euler method (solving principle is demonstrated in Example 10.5)

Example 10.5. Degradation of contaminant A (A↔P) follows second-order kinetics (r = k·c2) and it is performed in a batch rector. If the reaction rate constant of component A degradation is k = 2 1/h, and initial component concentrations is cA,0 = 1 mol/L and cP,0 = 0 mol/L calculate change in concentration of both components using: a. Euler method b. Runge method c. Runge–Kutta method Develop dynamic mathematical model for both components. Calculate the first three steps of each method; define method step and all the assumptions necessary for solving this problem. Process system: – Batch reactor – second-order kinetics A!P

Figure (a): Batch reactor. Purpose/goal of modeling: To calculate concentration of components A and C Defining the mechanisms: Chemical reactions (A↔P), second-order kinetics (r = k·c2) Information’s about the process system: k = 2 1/h, cA,0 = 1 mol/L, cP,0 = 0 mol/L Model assumptions: – ideal mixing – V = const.; T = const.; Δ = const. Mass balances:

dcA dt

= − k
cA ) y , ðcA,0 Þ = − k
cA ;

Euler method: h = 0.1 t0 = 0 cA,0 = 1 mol/L cP,0 = 0 mol/L t1 = t0+ h = 0 + 0.1 = 0.1 h cA,1 = cA,0 + h·y´(cA,0) = 1 + 0.1·(−2 · 1) = 0.8 mol/L cP,1 = cP,0 + h·y´(cP,0) = 0 + 0.1·(2 · 1) = 0.2 mol/L t2 = t1+ h = 0.1 + 0.1 = 0.2 h cA,2 = cA,1 + h·y´(cA,1) = 0.8 + 0.1·(−2 · 1) = 0.64 mol/L

dcP dt

= k
cA

) y , ðcP,0 Þ = k
cA

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10 Modeling of environmental processes

cP,2 = cP,1 + h·y´(cP,1) = 0.2 + 0.1·(2 · 1) = 0.36 mol/L Runge method: h = 0.1 t0 = 0 cA,0 = 1 mol/L cP,0 = 0 mol/L t1 = t0+ h = 0 + 0.1 = 0.1 h for cA,1:

for cP,1:

g1,1 cA = y ðt0 , cA,0 Þ = − k
cA,0

g1,1 cP = y ðt0 , cP,0 Þ = k
cA,0 = 2
1 = 2

= −2
1= −2 y1 − 1=2 cA

= cA,0 + h2
g1,1 cA = 1 +

0.1 2


ð − 2Þ = 0.9

g2,1 cA = yðt0 + h2 , y1 − 1=2 cA Þ = − k
y1 − 1=2 cA = − 2
0.9 = − 1.8

y1 − 1=2 cP = cP,0 + h2
g1,1 cP 0.1 2
2 = 0.1 h cA , 2 y1 − 1=2 Þ

=0+ g2,1

cP

= yðt0 +

= k
y1 − 1=2 cA = 2
0.9 = 1.8 cP,1 = cP,0 + h
g2,1 cP

cA,1 = cA,0 + h
g2,1 cA = 1 + 0.1
ð − 1.8Þ = 0.82 mol=L t2 = t1+ h = 0 + 0.1 = 0.2 h for cA,2: g1,2 cA = y ðt1 , cA,1 Þ = − k
cA,1

= 0 + 0.1
1.8 = 0.18 mol=L for cP,2: g1,2 cP = y ðt1 , cP,1 Þ

= − 2
0.82 = − 1.64

= k
cA,1 = 2
0.82 = 1.64

y2 − 1=2 cA = cA, 1 + h2
g1,2 cA 0.1 = 0.82 +
ð − 1.64Þ = 0.738 2   h g2,2 cA = y t1 + , y2 − 1=2 cA = − k
y2 − 1=2 cA 2 = − 2
0.738 = − 1.476 cA,2 = cA,1 + h
g2,2 cA

h
g1, 2 cP 2 0.1 = 0.18 +
1.64 = 0.262 2 h g2,2 cP = yðt0 + , y2 − 1=2 cA Þ 2 = k
y1 − 1=2 cA = 2
0.738 = 1.476

y2 − 1=2 cP

= cP, 1 +

cP,2 = cP,1 + h
g2,2 cP

= 0.82 + 0.1
ð − 1.476Þ = 0.6724 mol=L

= 0.18 + 0.1
1.476 = 0.3276 mol=L

Runge–Kutta method: h = 0.1 t0 = 0 cA,0 = 1 mol/L cP,0 = 0 mol/L t1 = t0+ h = 0 + 0.1 = 0.1 h for cA,1: g1,1 cA = h
f ðt0 , cA,0 Þ = h
ð − k
cA,0 Þ = 0.1
ð − 2
1Þ = − 0.2 ! c c g2,1 cA = h
f t0 + h2 , cA,0 +

g A 1,1 2

g3,1 cA = h
f t0 + h2 , cA,0 +

c g A 2,1 2

= h
ð − k
ðcA,0 +

g A 1,1 2 ÞÞ = 0.1


ð − 2
ð1 +

− 0.2 2 ÞÞ =

= h
ð − k
ðcA,0 +

c g A 2,1 2 ÞÞ = 0.1


ð − 2
ð1 +

− 0.18 2 ÞÞ =

!

− 0.18 − 0.182

  cA cA = h
ð − k
ðcA, 0 + g3,1 ÞÞ = 0.1
ð − 2
ð1 + ð − 0.182ÞÞ = − 0.1636 g4,1 cA = h
f t0 + h, cA,0 + g3,1 cA,1 = cA,0 + 61
ðg1,1 cA + 2
g2,1 cA + 2
g3,1 cA + g4,1 cA Þ = 0.8188 mol=L

10.4 Balance equations – Solving mathematical models

341

for cP,1: g1,1 cP = h
f ðt0 , cA,0 Þ = h
k
cA,0 ! = 0.1
2
1 = 0.2 g2,1 cP = h
f t0 + h2 , cA,0 +

c g A 1,1 2

c g A

= h
k
ðcA,0 + !

c g A 1,1 2

Þ = 0.1
2
ð1 +

− 0.2 2 Þ = 0.18

c g A

− 0.182 = h
k
ðcA,0 + 2,1 g3,1 cP = h
f t0 + h2 , cA,0 + 2,1 2 Þ = 0.182 2 2 Þ = 0.1
2
ð1 +   cA cA = h
k
ðcA,0 + g3,1 Þ = 0.1
2
ð1 + ð − 0.182Þ = 0.1636 g4,1 cA = h
f t0 + h, cA,0 + g3,1

cP,1 = cP,0 + 61
ðg1,1 cP + 2
g2,1 cP + 2
g3,1 cP + g4,1 cP Þ = 0.1813 mol=L t2 = t1+ h = 0 + 0.1 = 0.2 h for cA,2: g1,2 cA = h
f ðt1 , cA,1 Þ = h
ð − k
cA,0 Þ = 0.1
ð − 2
0.8188Þ = − 0.1638 ! cA c g1,2 gA h cA g2,2 = h
f t1 + , cA,1 + = h
ð − k
ðcA,1 + 1,2 ÞÞ 2 2 2 − 0.1638 = 0.1
ð − 2
ð0.8188 + ÞÞ = − 0.1474 2 cA ! c g gA h g3,2 cA = h
f t1 + , cA,1 + 2,2 = h
ð − k
ðcA,1 + 2, 2 ÞÞ 2 2 2 − 0.1474 ÞÞ = − 0.1490 = 0.1
ð − 2
ð0.8188 + 2   cA cA ÞÞ = h
ð − k
ðcA,1 + g3,2 g4,2 cA = h
f t1 + h, cA,1 + g3,2 = 0.1
ð − 2
ð0.8188 + ð − 0.1490ÞÞ = − 0.1340 1 cA,2 = cA,1 +
ðg1,2 cA + 2
g2,2 cA + 2
g3,2 cA + g4,2 cA Þ = 0.6704 mol=L 6 for cP,2: g1,2 cP = h
f ðt1 , cA,1 Þ = h
k
cA,1 = 0.1
2
0.8188 = 0.1638 cA ! c g1,2 gA h − 0.1638 cP g2,2 = h
f t1 + , cA,1 + = h
k
ðcA,1 + 1,2 Þ = 0.1
2
ð0.8188 + Þ = 0.1474 2 2 2 2 ! c c gA gA h − 0.1474 Þ = 0.1490 g3,2 cP = h
f t1 + , cA,1 + 2,2 = h
k
ðcA,1 + 2,2 Þ = 0.1
2
ð0.8188 + 2 2 2 2   cA cA = h
k
ðcA,1 + g3,2 Þ = 0.1
2
ð0.8188 + ð − 0.1490Þ = 0.134 g4,2 cA = h
f t1 + h, cA,1 + g3,3 cP,2 = cP,1 +

1
ðg1,2 cP + 2
g2,2 cP + 2
g3,2 cP + g4,2 cP Þ = 0.3297mol=L 6

For solving partial differential equations mostly the used methods are: – Numerical methods – Transport phenomena are mostly described with mathematical models in the form of partial differential equations. The aim of solving partial differential equations is finding the function and boundary conditions that satisfy the relationships between different derivations in specific space and/ or time [12]. It is very complicated to get the solution that satisfies differential equations for analyzed dimension and that is why numerical methods based on the discrimination are used. Most frequently used are: method of lines, FDM, FEM, FVM and method of collocations.

342

10 Modeling of environmental processes

–

–

–

–

Method of lines (solving principle is demonstrated in Example 10.6) is semidiscretization method. It is based on the discretization in one dimension. After the discretization, the obtained system of differential equation is solved by using one of the methods for the solution of the differential equations. The FDM (solving principle is demonstrated in Example 10.6) is based on the approximation of the derivates with the series of algebraic equations using the Taylor’s polynomial [13]. Precision of the method is enlarged by using more components of the Taylor’s polynomial and by reducing the distance between the nods of the discretization. Using the described procedure continuous variables are replaced by discrete variables and the obtained solution is not continuous for the whole analyzed domain but values for the discrete nods (points) are obtained. For nonlinear systems after the discretization, the series of the nonlinear algebraic equations is obtained that can be solved using Newton method. Finite difference discretization can be performed: (i) approximation in three points forward, (ii) approximation in three points backward and (iii) approximation in three central points. FEM is used for the solution of the problems of the field. It cuts a structure into several elements (pieces of the structure) and then reconnects elements at nodes as if nodes were pins that hold elements together. This procedure results in a set of simultaneous algebraic equations. FVM is a discretization technique for partial differential equations that are developed from physical conservation laws. This method uses a volume integral formulation of the problem with a finite partitioning set of volumes to discretize the equations. FVM is in common use for discretizing computational fluid dynamics equations [14].

Example 10.6. In case of the discharge of the pollutants in the river, organic compounds are degraded by aerobic microorganisms presented in the river. The organic compound consumption causes dissolved oxygen concentration reduction in the river. Oxygen consumption takes place parallel with the oxygen transfer from the gas phase to the liquid through interfacial area. With the assumption that the river estuary can be modeled as the ideal tubular reactor analyze the change of the organic compound concentrations and dissolved oxygen concentration over the time and position. The organic compound degradation can be described with the Monod kinetics. Parameters of the Monod kinetics are: maximum specific growth rate µ = 0.05 1/h and Monod constant KS = 0.0001 g/L. Average river velocity is v = 7500 dm/h. Ratio of the organic compound degradation over the oxygen consumption is YS/O = 0.2 and ratio of the biomass growth over the organic compound degradation is YX/S = 1. Initial concentration of the organic compounds is cS0 = 0.04 g/L, the initial concentration of the biomass is cX,0 = 0.002 g/L, oxygen saturation concentration is cO,s = 0.0087 g/L and oxygen transfer rate is kLa = 0.025 1/h. a. Develop the balances for the organic compound change, dissolved oxygen concentration change and biomass concentration change over the time and position. b. Solve the balances using the method of lines.

10.4 Balance equations – Solving mathematical models

343

(a) Balances for the change of organic compound concentration, dissolved oxygen concentration and biomass concentration over the time and position. ðt, x Þ ± r ðγðt, x ÞÞ General expression for the balances in ideal the ideal tubular reactor: ∂γð∂tt, x Þ = − v
∂γ∂x ∂γS ðt, x Þ ∂γ ðt, x Þ γ ðt, x Þ = − v
S∂x − Y 1 μmax
Ks +s γ ðt, xÞ ∂t s X=S γs ðt, x Þ ∂γx ðt, x Þ − v
∂x + μmax
Ks + γ ðt, xÞ
γX ðt, x Þ s

Organic compounds concentration change: Biomass concentration change:

∂γx ðt, x Þ ∂t

=

Dissolved oxygen concentration change:   ∂γ ðt, x Þ γ ðt, x Þ = − v
O∂x + kL a
γ0S − γ0 − Y 1
μmax
Ks +s γ ðt, xÞ
γX ðt, x Þ

∂γO ðt, x Þ ∂t

s

S=O

(b) Solution of the balances using the method of lines. ðt, x Þ Discretization of the first derivation: ∂γ∂x = γðt, x + hhÞ − γðt, xÞ Step of the discretization: h = 0.1 Discretised form of balances: ∂γS, 0 ∂t ∂γS, 1 ∂t

=0 = −v


γS, 1 − γS, 0 h


μmax
∂γS, 2 ∂t

= −v


.. . ∂γS, 10 ∂t

γS, 1 KS + γS, 1

γS, 2 − γS, 1 h


μmax


= −v


γS, 2 KS + γS, 2

∂γO, 2 ∂t

.. .

∂γO, 10 ∂t

γO, 1 − γO, 0 h

= −v


γO, 2 − γO, 1 h

= −v


−

1 YX=S


γX, 2

γS, 10 KS + γS, 10




= −v


γX, 1 − γX, 0 h

+ μmax
K

∂γX, 2 ∂t

= −v


γX, 2 − γX, 1 h

+ μmax
K

=0 γS, 1 S + γS, 1


γX, 1

γS, 1 S + γS, 1


γX, 2 .


γX, 1

γS, 10 − γS, 9 h


μmax
∂γO0 ∂t = 0 ∂γO, 1 ∂t = − v

−

1 YX=S

∂γX, 0 ∂t ∂γX, 1 ∂t

−

1 YX=S

.. . ∂γX, 10 ∂t

= −v


γX, 10 − γX, 9 h

γS, 1 S + γS, 1

+ μmax
K


γX, 10

  γ + kL a
γO, S − γO, 1 − Y 1
μmax
K +S,γ1
γX, 1 S S, 1 S=O   γ + kL a
γO, S − γO, 2 − Y 1
μmax
K +S,γ1
γX, 2

γO, 10 − γO, 9 h

S=O

  + kL a
γO, S − γO, 9 −

1 YS=O

S

S, 1

γS, 1 S + γS, 1


μmax
K


γX, 10

Wolfram Mathematica 10.1. Code μmax = 0.05; Ks = 0.0001; Yso = 0.2; Yxs = 1; kLa = 0.025;1 cOs = 0.0087; h = 350; tf = 100; model = NDSolve[{cS0[t] = = 0, cS1[t] = = -v*(cS1[t]-cS0[t])/h-1/Yxs*μmax*cS1[t]/(Ks+cS1[t])*cX1[t], cS2[t] = = -v*(cS2[t]-cS1[t])/h-1/Yxs*μmax*cS2[t]/(Ks+cS2[t])*cX2[t], cS3[t] = = -v*(cS3[t]-cS2[t])/h-1/Yxs*μmax*cS3[t]/(Ks+cS3[t])*cX3[t], cS4[t] = = -v*(cS4[t]-cS3[t])/h-1/Yxs*μmax*cS4[t]/(Ks+cS4[t])*cX4[t], cS5[t] = = -v*(cS5[t]-cS4[t])/h-1/Yxs*μmax*cS5[t]/(Ks+cS5[t])*cX5[t], cS6[t] = = -v*(cS6[t]-cS5[t])/h-1/Yxs*μmax*cS6[t]/(Ks+cS6[t])*cX6[t], cS7[t] = = -v*(cS7[t]-cS6[t])/h-1/Yxs*μmax*cS7[t]/(Ks+cS7[t])*cX7[t],


γX, 10


γX ðt, x Þ

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10 Modeling of environmental processes

cS8[t] = = -v*(cS8[t]-cS7[t])/h-1/Yxs*μmax*cS8[t]/(Ks+cS8[t])*cX8[t], cS9[t] = = -v*(cS9[t]-cS8[t])/h-1/Yxs*μmax*cS9[t]/(Ks+cS9[t])*cX9[t], cS10[t] = = -v*(cS10[t]-cS9[t])/h-1/Yxs*μmax*cS10[t]/(Ks+cS10[t])*cX10[t], cX0[t] = = 0, cX1[t] = = -v*(cX1[t]-cX0[t])/h+μmax*cS1[t]/(Ks+cS1[t])*cX1[t], cX2[t] = = -v*(cX2[t]-cX1[t])/h+μmax*cS2[t]/(Ks+cS2[t])*cX2[t], cX3[t] = = -v*(cX3[t]-cX2[t])/h+μmax*cS3[t]/(Ks+cS3[t])*cX3[t], cX4[t] = = -v*(cX4[t]-cX3[t])/h+μmax*cS4[t]/(Ks+cS4[t])*cX4[t], cX5[t] = = -v*(cX5[t]-cX4[t])/h+μmax*cS5[t]/(Ks+cS5[t])*cX5[t], cX6[t] = = -v*(cX6[t]-cX5[t])/h+μmax*cS6[t]/(Ks+cS6[t])*cX6[t], cX7[t] = = -v*(cX7[t]-cX6[t])/h+μmax*cS7[t]/(Ks+cS7[t])*cX7[t], cX8[t] = = -v*(cX8[t]-cX7[t])/h+μmax*cS8[t]/(Ks+cS8[t])*cX8[t], cX9[t] = = -v*(cX9[t]-cX8[t])/h+μmax*cS9[t]/(Ks+cS9[t])*cX9[t], cX10[t] = = -v*(cX10[t]-cX9[t])/h+μmax*cS10[t]/(Ks+cS10[t])*cX10[t], cO0[t] = = 0, cO1[t] = = -v*(cO1[t]-cO0[t])/h+kLa*(cOs-cO1[t]) 1/Yso*μmax*cS1[t]/(Ks+cS1[t])*cX1[t], cO2[t] = = -v*(cO2[t]-cO1[t])/h+kLa*(cOs-cO2[t])-1/Yso*μmax*cS2[t]/(Ks+cS2[t])*cX2[t], cO3[t] = = -v*(cO3[t]-cO2[t])/h+kLa*(cOs-cO3[t])-1/Yso*μmax*cS3[t]/(Ks+cS3[t])*cX3[t], cO4[t] = = -v*(cO4[t]-cO3[t])/h+kLa*(cOs-cO4[t])-1/Yso*μmax*cS4[t]/(Ks+cS4[t])*cX4[t], cO5[t] = = -v*(cO5[t]-cO4[t])/h+kLa*(cOs-cO5[t])-1/Yso*μmax*cS5[t]/(Ks+cS5[t])*cX5[t], cO6[t] = = -v*(cO6[t]-cO5[t])/h+kLa*(cOs-cO6[t])-1/Yso*μmax*cS6[t]/(Ks+cS6[t])*cX6[t], cO7[t] = = -v*(cO7[t]-cO6[t])/h+kLa*(cOs-cO7[t])-1/Yso*μmax*cS7[t]/(Ks+cS2[t])*cX7[t], cO8[t] = = -v*(cO8[t]-cO7[t])/h+kLa*(cOs-cO8[t])-1/Yso*μmax*cS8[t]/(Ks+cS8[t])*cX8[t], cO9[t] = = -v*(cO9[t]-cO8[t])/h+kLa*(cOs-cO9[t])-1/Yso*μmax*cS9[t]/(Ks+cS9[t])*cX9[t], cO10[t] = = -v*(cO10[t]-cO9[t])/h+kLa*(cOs-cO10[t])-1/Yso*μmax*cS10[t]/(Ks+cS10[t])*cX10[t], cS0[0] = = 0.040, cS1[0] = = 0,cS2[0] = = 0,cS3[0] = = 0,cS4[0] = = 0,cS5[0] = = 0, cS6[0] = = 0,cS7[0] = = 0,cS8[0] = = 0,cS9[0] = = 0,cS10[0] = = 0,cX0[0] = = 0.002, cX1[0] = = 0,cX2[0] = = 0,cX3[0] = = 0, cX4[0] = = 0,cX5[0] = = 0,cX6[0] = = 0, cX7[0] = = 0,cX8[0] = = 0,cX9[0] = = 0,cX10[0] = = 0,cO0[0] = = 0.0078,cO1[0] = = 0, cO2[0] = = 0,cO3[0] = = 0,cO4[0] = = 0,cO5[0] = = 0,cO6[0] = = 0,cO7[0] = = 0, cO8[0] = = 0,cO9[0] = = 0,cO10[0] = = 0},{cS0,cS1,cS2,cS3,cS4,cS5,cS6,cS7,cS8,cS9,cS10,cX0,cX1, cX2,cX3,cX4,cX5,cX6,cX7,cX8,cX9,cX10,cO0,cO1,cO2,cO3,cO4, cO5,cO6,cO7,cO8,cO9,cO10},{t,0,tf}]; kcS0[t_]: = cS0[t]/.model kcS1[t_]: = cS1[t]/.model kcS2[t_]: = cS2[t]/.model kcS3[t_]: = cS3[t]/.model kcS4[t_]: = cS4[t]/.model kcS5[t_]: = cS5[t]/.model kcS6[t_]: = cS6[t]/.model kcS7[t_]: = cS7[t]/.model kcS8[t_]: = cS8[t]/.model kcS9[t_]: = cS9[t]/.model kcS10[t_]: = cS10[t]/.model kcX0[t_]: = cX0[t]/.model kcX1[t_]: = cX1[t]/.model kcX2[t_]: = cX2[t]/.model kcX3[t_]: = cX3[t]/.model kcX4[t_]: = cX4[t]/.model kcX5[t_]: = cX5[t]/.model kcX6[t_]: = cX6[t]/.model kcX7[t_]: = cX7[t]/.model kcX8[t_]: = cX8[t]/.model kcX9[t_]: = cX9[t]/.model kcX10[t_]: = cX10[t]/.model kcO0[t_]: = cO0[t]/.model kcO1[t_]: = cO1[t]/.model kcO2[t_]: = cO2[t]/.model kcO3[t_]: = cO3[t]/.model kcO4[t_]: = cO4[t]/.model kcO5[t_]: = cO5[t]/.model kcO6[t_]: = cO6[t]/.model kcO7[t_]: = cO7[t]/.model kcO8[t_]: = cO8[t]/.model kcO9[t_]: = cO9[t]/.model kcO10[t_]: = cO10[t]/.model Plot[{kcS0[t],kcS1[t],kcS2[t],kcS3[t],kcS4[t],kcS5[t],kcS6[t],kcS7[t],kcS8[t],kcS9[t],kcS10[t]},{t,0,tf}, AxesLabel->{“t/h”,”γS/gL-1”}]

10.4 Balance equations – Solving mathematical models

345

Plot[{kcX0[t],kcX1[t],kcX2[t],kcX3[t],kcX4[t],kcX5[t],kcX6[t],kcX7[t],kcX8[t],kcX9[t],kcX10[t]},{t,0,tf}, AxesLabel->{“t/h”,”γX/gL-1”},] Plot[{kcO0[t],kcO1[t],kcO2[t],kcO3[t],kcO4[t],kcO5[t],kcO6[t],kcO7[t],kcO8[t],kcO9[t],kcO10[t]},{t,0, tf},AxesLabel->{“t/h”,”γ0/gL-1”}] Print[“supstrate concententration”,kcS10[tf]] Print[“biomass concententration”,kcX10[tf]] Print[“dissolved oxygen concententration”,kcO10[tf]] 2.6 40.0

2.5 39.8

2.4 2.3

39.6

2.2

39.4

2.1 39.2

2.0 39.0 0

200

400

600

800

1000

t (h)

1.9 0

200

400

600

800

1000

t (h)

Figure (f): Organic compound concentration change over the time.

Figure (g): Biomass concentration change over the time.

9.0

supstrate concententration {0.0399528} biomass concententration {0.00204715} dissolved oxygen concententration {0.00663523}

8.5 8.0 8.5 7.0 6.5 6.0 0

200

400

600

800

1000

t (h)

Figure (h): Dissolved oxygen concentration change over the time. Example 10.7. After treatment, the surface of the soil with the pesticide the distribution of the pesticide over the time and space was analysed in the segment of the soil to depth of 0.5 m (root zone). It is known that change of the concentration of pesticide depends on the diffusion, convection, microbial degradation, plat uptake, leaching and adsorption. The plat uptake, leaching and adsorption process can be described with first-order kinetics (k1(plant uptake rate) = 0.084 1/day, k2(leaching) = 0.008 1/day, k3(adsorption) = 0.05 1/day), while microbial degradation is described with Monod kinetics. Parameters of the Monod kinetics are: maximum specific growth rate µmax = 0.09 1/day, and Monod constant KS = 0.000036 g/L. The biomass degradation is also included into the balance with biomass degradation rate of kd = 0.1881/day. Diffusion coefficient of the used pesticide is Dp = 2.44 ⋅ 10–4 dm2/day and water velocity is v = 0.001 m/day. Initial concentration of the dissolved pesticide is γS0 = 0.000066 g/L and initial biomass concentration is γX0 = 0.00034 g/L. a. Set the balances for the dissolved pesticide concentration change and for the biomass concentration change. b. Solve the balances using the FDM for time period of 20 day and soil segment depth of 0.5 m.

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10 Modeling of environmental processes

(a) Balances for the dissolved pesticide concentration change and for the biomass concentration change. ∂γpesticide ∂t

= Dp


∂2 γpesticide ∂x 2

−v


∂γpesticide ∂x

− μmax


γpesticide
γbiomass KS + cpesticide

− k1
γpesticide − k2
γpesticide − k3
γpesticide ∂γbiomass ∂t

= μmax


γpesticide
γbiomass KS + γpesticide

− kd
γbiomass

(b) Finite differences method. ∂γpesticide ∂t

= Dp


∂2 γpesticide ∂x 2

−v


∂γpesticide ∂x

− μmax


γpesticide
γbiomass KS + γpesticide

− k1
γpesticide − k2
γpesticide − k3
γpesticide γSi + 1, j − γSi − 1, j γSi, j + 1 − 2
γSi, j + γSi, j − 1 γSi, j + 1 − γSi, j − 1 = Dp
−v
2
ht h2x hx γSi, j
γXi, j − μmax
− k1
γSi, j − k2
γSi, j − k3
γSi, j KS + γSi, j  Dp
2
ht  γSi + 1, j − γSi − 1, j = 2
γSi, j + 1 − 2
γSi, j + γSi, j − 1 hx    γS
γX v
2
h  − hx t
γSi, j + 1 − γSi, j − 1 − μmax
2
ht
K i,+j γS i, j − S

As =

Dp
2
ht h2 x

Bs =

v
2
ht hx

i, j

− ðk1
2
ht Þ
γSi, j − ðk2
2
ht Þ
γSi, j − ðk3
2
ht Þ
γSi, j   Cs = μmax
2
ht Ds = ðk1
2
ht Þ Es = ðk2
2
ht Þ

Fs = ðk3
2
ht Þ   γSi + 1, j − γSi − 1, j = As
γSi, j + 1 − 2
γSi, j + γSi, j − 1   γSi, j
γXi, j − Bs
γSi, j + 1 − γSi, j − 1 − Cs
− Ds
γSi, j − Es
γSi, j − Fs
γSi, j KS + γSi, j   γSi + 1, j − γSi − 1, j = As
γSi, j + 1 − 2
γSi, j + γSi, j − 1   − Bs
γSi, j + 1 − γSi, j − 1 γSi, j
γXi, j − Cs
− Ds
γSi, j − Es
γSi, j − Fs
γSi, j KS + γSi, j γSi, j =

ðAs − BsÞ ð2
As + Ds + Es + FsÞ

−


γSi, j + 1 +

Cs ð2
As + Ds + Es + FsÞ




γSi, j
γXi, j KS + γSi, j

ðAs + BsÞ ð2
As + Ds + Es + FsÞ

−−


γSi, j − 1

1 ð2
As + Ds + Es + FsÞ

  γSi + 1, j − γSi − 1, j

ð2
As + Ds + Es + FsÞ
γSi, j = ðAs − BsÞ
γSi, j + 1 + ðAs + BsÞ
γSi, j − 1 − Cs


 γSi, j
γXi, j  − γSi + 1, j − γSi − 1, j KS + γSi, j

Wolfram Mathematica 10.1. eqnsS = Table[cSi,j = = (As-Bs)/ Code (2*As+Cs+Es+Fs)*cSi,j+1+(As+Bs)/ dP = 24.4*10–5; (2*As+Cs+Es+Fs)*cSi,j-1Ds/ time = 20; (2*As+Cs+Es+Fs)*(cSi,j*cXi,j)/ (Ks+cSi,j)-1/(2*As+Cs+Es+Fs)*(cSi+1,j-cSi-1,j)/. depth = 0.5; {x->ξi,y>ηj},{i,nx-1},{j,ny-1}];

10.5 Conclusion

eqnsX = Table[cXi,j = = Ax/Bx*(cSi,j*cXi,j)/(cSi,j+Ks)-1/Bx*(cXi+1,j-cXi-1,j)/.{x->ξi,y->ηj},{i,nx-1}, {j,ny-1}] boundS1 = Table[{(cSi,0-cSi-1,1)/hy = = 0/.x->ξi,(cSi,ny - cSi-1,ny-1)/hy = = 0/.x->ξi},{i,nx-1}]; boundS2 = Table[{cS0,j = = cS0/.y->ηj,(cSnx, j - cSnx - 1, j)/hx = = 0/.y->ηj},{j,0,ny}]; boundX1 = Table[{(cXi,0-cXi-1,1)/hy = = 0/.x->ξi,(cXi, ny - cXi-1, ny-1)/hy = = 0/.x->ξi},{i,nx-1}] boundX2 = Table[{cX0,j = = cX0/.y->ηj,(cXnx, j - cXnx-1, j)/hx = = 0/.y->ηj}, {j,0,ny}] uapprS = ListInterpolation[solS,{{0,time}, {0,depth}}] Plot3D[uapprS[x,y],{x,0,time},{y,0,depth}, ViewPoint->{2.0,-2.4,0.9}, AxesStyle->{Directive[Black,12,Bold],Directive[Black,12,Bold], Directive[Black,12,Bold]},Ticks->{{0,5,10,15,time}, {0,0.1,0.2,0.3,0.4,0.5},{0,1,2,3,4,5}}] l/m

0

0.5 0.3 0.4 0.1 0.2

γ / g L-1

v = 0.1/10,000; k1 = 0.084; mimax = 0.0916; k3 = 0.008; k4 = 0.05; kd = 0.188; Ks = 0.035574; cS0 = 0.066; cX0 = 0.34; x0 = 0; x1 = time; y0 = 0; y1 = 0.5; nx = 5; ny = 5; hx = N[(x1-x0)/nx] hy = N[(y1-y0)/ny] Do[ξi = x0 + i hx,{i,0,nx}] Do[ηj = y0 + j hy,{j,0,ny}] varsS = Table[cSi,j,{i,0,nx}, {j,0,ny}]; As = (2*hx*dP)/(hy*hy) Bs = (2*hx*v)/hy Cs = k1*2*hx Ds = mimax*2*hx Es = k3*2*hx Fs = k4*2*hx Ax = mimax*2*hx; Bx = kd*2*hx;

347

0

0

5 t / day

10 15 20

Figure (i): Pesticide concentration change over the time and depth.

10.5 Conclusion In the end, we can just say that writing this chapter was not easy. Trying to summarize mathematical modelling in just one chapter was something similar with trying to develop a process mathematical model. A lot of inlet information, a lot of approaches, a lot of connections between them and all of that just to get a simple model that only approaches to the real problem. We are aware that this is just a small introduction to mathematical modeling but we hope that we inspired and encouraged you to go and explore all the possibilities that are in front of you. Always have in mind that this is not simple field and it demands a lot of previous knowledge but as Lord Kelvin said: “I can never satisfy myself until I can make a model of a thing. If I can make a model, I can understand it.” Chase the knowledge.

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Important notification For preparation of this chapter, classroom materials from University of Zagreb, Faculty of Chemical Engineering and Technology, course Analysis and modelling of the processes held by prof. B. Zelić were used along with many books considering modeling and mathematical modeling. For additional information, we encourage you to go through books listed in the literature. All the examples (solved and for practice) were created by the authors of this chapter. Acknowledgement: The authors would like to take this opportunity to express their gratitude to the reviewers’ constructive comments and advice. All suggestions are more than welcome, especially when they amplify the quality of the work. Each reviewer comment has been discussed separately followed by the answers. All accepted remarks after first revision have been incorporated directly into the final version of the text and are marked yellow.

References [1] [2] [3] [4] [5] [6] [7] [8] [9] [10] [11] [12] [13] [14]

Hangos K, Cameron I. Process modelling and model analysis. UK: Academic press, 2001: 1–33. Plazl I, Lakner M. Uvod v modeliranje procesov,Taložba FKKT. Slovenia: Univerza v Ljubljani, 2004: 1–48. Himmelblau DM, Bishoff KB. Process analysis and simulation. New York: Wiley, 1968. Davis ME. Numerical methods and modelling for chemical engineers. New York: Wiley, 1984. Riggs JB. An introduction to numerical methods for chemical engineers, 2nd ed. Texas: Texas University Press, 1994. Rice RD, Do DD. Applied mathematics and modelling for chemical engineers. New York: Wiley, 1995. Aris R. Mathematical modeling techniques. London: Pitman, 1978. Denn MM. Process modelling. New York and London: Longman, 1986. Mathematical QA. Models in science and engineering. Notices of the AMS. 2009;56(1): 10–19. Pritsker A Why simulation works, Proceedings on the 1989 Winter Simulation Conference, 1–6. Dym CL. Principles in mathematical modeling. California: Elsevier, 2004: 1–10. Payre G. Influence graphs and the generalized finite difference method. Comput Methods Appl Mech Eng. 2007;196:1933–45. Botte GG, Ritter JA, White RE. Comparison of finite difference and control volume methods for solving differential equations. Comp Chem Eng. 2000;24:2633–54. Toh KC, Chen XY, Chai JC. Numerical computation of fluid flow and heat transfer in microchannels. Int J Heat Mass Tran. 2002;45:5133–41.

Examples for practice Example 1: The liquid phase reaction A↔B is carried out in batch reactor. In a first minute, a reaction initial concentration of reactant A drops from 1.5 mol/L to 1 mol/L.

Examples for practice

349

What is the reaction rate and what is the time necessary to achieve conversion of 95 % if the kinetic is (a) first order and (b) second order with respect to reactant? Graphically describe dynamic change of concentration. Due to market demands, continuous stirred tank reactor, CSTR, also needs to be tested for the same reaction. What is the volume of that reactor, necessary to achieve the same conversion if the volumetric flow rate of the reactant A is 0.5 L/min and the reaction rates are the same as the one estimated in the previous step? Graphically describe dynamic change from initial to stationary phase and determine hydraulic retention time necessary to achieve mentioned efficiency. Solution: Batch: a. kd = 0.405 mol/L⋅min; t = 7.39 min b. kd = 0.333 mol/L⋅min; t = 38.03 min

CSTR: a. V = 23.45 L; τ = 46.91 min b. V = 760.76 L; τ = 1521.7 min Example 2: Wastewater passes through seven (7) tubular plug flow reactors connected into a series. Length of each reactor is 10 m with cross-section area of 100 dm2. Water is polluted by component A (0.010 g/L) that is introduced into the reactor with flow rate of 80 dm2/s. Reaction rate constant is 0.055 L/g s and the process of the pollutant removal is described with second-order kinetics. How many plug flow reactors have to be connected into a series to achieve 95 % and 99 % pollutant A removal? Graphically describe dynamic change of concentration along length of plug flow reactors. Solution: a. N = 6 reactors for 95 % efficiency b. N = 29 reactors for 99 % efficiency (not possible to achieve at present conditions)

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10 Modeling of environmental processes

Example 3: Lavender incense stick is burning in a closed room (V = 50,000 L) for 20 minutes. In that time, it releases 50 mg of scent particles in a room. A person which does not like the smell of lavender enters a room and opens the window. If the ventilator is working in the room for 20 min will that be enough to minimize the smell (particles concentration below 0.020 µg/L) so a person can come back to the room? Predict the dynamic change of particle concentration in the room. Solution: t = 20 min, γparticles = 3 · 10–7 g/L (limit γparticles = 0.00002 g/L)

Example 4: A mobile phone indicates that the battery is low (5 %) and that charging is necessary. Speed of charging is 2.1 %/min. During the first 10 min the phone is just charging but after that the user becomes inpatient and opens several applications. One is using 0.5 %/min, second 0.02 %/min and third 0.2 %/min of battery. How long will it take the battery to fully charge if after 10 min of parallel use application 1 is shut down, after 20 min application 2 and 5 min after the last one is closed? Describe the dynamic change of charging in time.

Examples for practice

351

Solution: t = 51 min

Example 5: During the summer season in some wells level of water can decrease. By decreasing the level of water, concentrations of some compounds harmful for human’s, increases. Due to that water becomes harmful for human consumption. Assume a well with inner diameter of 15 dm and the depth of water 40 dm at the beginning of dry season. Concentration of harmful compounds is 0.000001 mmol/L, which is 1000 times lower than the prescribed limit for drinking water. If water evaporates with the rate of 0.70 mol/dm2 h, determine the depth of water after which water will become harmful for human consumption. Solution: t = 35.83 day h = 51.75 dm

Example 6: After washing the factory for candy production, wastewater analysis showed that this water is not suitable for direct realizing into the nearby river. Due to that, all the water was collected into a tank for microbial wastewater treatment.

352

10 Modeling of environmental processes

Mixed microbial culture (biomass, γx = 0.010 g/L) present in the tank follows Monod kinetics for organic waste (substrate) removal (γs = 0.3 g/L). Define mathematical model that will describe organic waste removal and biomass growth if the estimated kinetic parameters are µmax = 5 d−1, Ks = 0.045 g/L, kd = 0.002 h−1 and Yx/s = 0.8 g/g. Calculate how much time will it take to remove 90 % of initial organic waste. After what time will biomass start dying? How longer will it take to achieve the same efficiency if after second production cycle concentration of organic waste in the water is 6.7-fold higher? After the first cycle (t = 2 h), 75 % of the biomass was removed from the tank and the rest was used for the second cycle. Solution: a. t (for 90 % efficiency) = 0.706 ht (biomass dying) = 1.5 h b. t = 0.656 h

Example 7: Wastewater purification system based on active biomass (γx = 0.001 g/L) is included in building planes of new factory. Expected amount of organic waste (BOD = Biochemical oxygen demand) was calculated to be γBOD = 0.5 g/L. Preliminary research demonstrated that present microbial culture follows Monod kinetics with estimated kinetic parameters: µmax = 2 d−1, Ks = 0.025 g/L, kd = 0.008 h−1 and Yx/s = 0.5 g/g. In order to release water in the environment purification efficiency has to be 97 %. Possible solution is one of three reactors: a. Batch reactor b. Continuous stirred tank reactor (V = 1.5 · 106 m3, q = 5000 L/h) c. Fed-batch reactor (V = 5 · 105 L) where the substrate is introduced into the reactor with flow rate of 1000 L/h. For all stirred tank reactors only 75 % of total volume is allowed to be used. What is the best solution?

Examples for practice

353

Solution: a. Batch: t = 2.97 h b. CSTR: t = 2.96 h (but 4τ = 1200 h) c. Fed batch: t = 3.36 h (but it takes 375 h to fill the complete reactor volume)

Example 8: A lake (V = 5 · 1013 L) is being polluted by two sources. One is the river coming from the north where a pig farm is placed and the second is the river coming from the west where a pesticide factory is releasing process water into the river. Concentration of pollutants that flows into the lake by the first river (qv = 1.5 · 1012 L/ year) is 0.150 g/L and by the second river (qv = 2.1 · 1010 L/year) is 0.082 g/L. Some plants that are present in the lake have the possibility to remove some of the organic compounds that are being released into the lake (incorporate pollutants like nitrogen in their metabolic pathway). That process can be described by first order kinetic with k = 0.02 year−1. If the pig farm was opened from 1975 to 2000 and pesticide farm from 1981 to 2016, determine the time period when water from the lake is suitable for drinking taking in consideration that the concentration of pollutant in the lake has to be below 0.025 g/L to be safe for human consumption. Assume that the volume of the lake is constant.

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10 Modeling of environmental processes

Solution: Time period from 1975 to 1981 and from 2019

Example 9: After the factory was closed, an artificial lake that was constructed to collect all the wastewater from factory has to be remediated. The concentration of heavy metals (HM) measured in the lake cHM = 300 mmol/L indicated severe pollution. Absorption on zeolite was proposed as a possible solution. During the preliminary measurements, it was determined that the average absorption velocity is 0.009 mmol/L h. Additionally, some heavy metal sedimentation was also noticed and it was determined to be 0.001 mmol/L h. Determine the time necessary to achieve 90 % and 95 % heavy metal removal from lake with assumption that the lake volume is constant. Demonstrate dynamics of heavy metals concentration change.

Solution: a. t (for achieving 90 % removal) = 3.08 g b. t (for achieving 95 % removal) = 3.25 g Example 10: In order to burn the waste where benzene is present in concentration of 150 mmol/L tubular incinerator (L = 10 m) was constructed. Reactor works at the temperature of 800 °C. Reaction kinetics is first order (k = 0.05 s−1). Arrhenius number was determined to be 7 · 109 s−1, while the activation energy is 200 kJ/mol. Determine

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if the constructed incinerator is sufficient to achieve 25 % conversion of benzene if the waste stream is entering with rate of 7.5 m/s and the residence time is 3 s. If it is not sufficient, how long it should be? Demonstrate the dynamic change of benzene concentration along incinerator length. Solution: cb = 26.99 mmol/L (at the exit; X = 82 %)

Hrvoje Kušić and Ana Lončarić Božić

11 Risk assessment Abstract: The chapter introduces risk assessment and examines the basic concepts of risk and hazard, their causes, consequences and probabilities. The methodology of environmental risk assessment including effect assessment, exposure assessment and risk estimation/characterisation is overviewed. Application of risk assessment for chemicals is described with regard to human health and the environment. Some of the commonly used techniques in risk assessments are introduced and illustrated by examples. Environmental risk assessment should provide input to the risk management so well-informed decisions can be made, to protect human health and the environment. Keywords: risk, hazard, environmental risk assessment, chemical risk, doseresponse, risk matrices, logic trees

11.1 Introduction 11.1.1 What is risk? According to the Merriam-Webster dictionary, word risk is defined as “possibility of loss or injury” and “someone or something that creates or suggests a hazard” [1]. Risk is also defined as “the possibility of incurring misfortune or loss; hazard” [2], “danger, or the possibility of danger, defeat, or loss” [3], “the possibility of suffering harm or loss; danger” and “a factor, thing, element, or course involving uncertain danger; a hazard” [4], “a situation involving exposure to danger” and “the possibility that something unpleasant or unwelcome will happen” [5]. Obviously, terms risk, hazard and possibility are closely related. In everyday life we are often faced to the “risky” situations which are characterised by uncertainty. Our action or choice can result with undesired consequences. Gambler choses to make a bet and takes a risk of losing the money. When a driver approaching the crossroad accelerates to pass through before the light turns red, he risks an accident or a ticket. Smokers voluntarily increase their health risk. The term risk is difficult to define precisely because it can be applied to a wide variety of situations and systems [6]. It is suggested that risk cannot be fully defined

This article has previously been published in the journal Physical Sciences Reviews. Please cite as: Lončarić Božić, A., Kušić, H. Risk Assessment. Physical Sciences Reviews [Online] 2018, 3. DOI: 10.1515/psr-2016-0126 https://doi.org/10.1515/9783110468038-011

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until the system itself has been chosen and defined. In such manner risk can be considered as a flexible term, adaptable to the situation in which it is being used. If the loss is something that is well understood, such as death, risk can be simply defined as the probability of that result [7]. In the contest of environmental risk assessment (ERA), risk is broadly defined as the likelihood that a harmful consequence will occur as the result of an action or condition [8, 9]. Generally, risk is a combination of the frequency or probability that the hazard will cause actual harm and the severity of the consequences. Accordingly, risk can be described by following expression: Risk = f ðFrequency or Probability, ConsequencesÞ

(11:1)

whereas both frequency/probability and the consequences refer to the specific hazardous event which is taking place [6]. 11.1.2 What is hazard? Rausand [10] describes hazard as a source of danger, being a property, a situation, or a state. Hazard is not an event but a prerequisite for the occurrence of a hazardous event that may lead to harm. Hazards can include substances, machines, energy forms, or the way certain activities are carried out. For example, a wet floor is a hazard as one could slip and fall. Moving parts of machinery represents a hazard that may cause injuries to the workers, which is often considered within occupational health and safety procedures. A fog is also a hazard as it reduces visibility in the traffic. Many chemicals have properties that make them hazardous such as toxicity, flammability, explosiveness, corrosiveness. However, the use of large amounts of dangerous chemicals is unavoidable in some industry sectors which are vital for a modern industrialised society. European Seveso III directive [11], aimed at the prevention of major accidents involving dangerous substances and at the mitigation of such events, defines hazard as intrinsic property of a dangerous substance or physical situation, with a potential for creating damage to human health or the environment. Hazard can be generally defined as the inherent potential for something to cause harm. Hazards are those things that might happen without saying how likely they are to happen. They are possibilities, without probabilities [12]. Hence, the term hazard can be defined as a function of both inherent properties and circumstances that may result in undesired outcome. The terms risk and hazards are often interchangeably used. A good and simple example of the distinction between the two could be found in the publication of European Environmental Agency [13]. “A large number of chemicals have hazardous properties. Acids may be corrosive or irritant to human beings for example.

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The same acid is only a risk to human health if humans are exposed to it. The degree of harm caused by the exposure will depend on the specific exposure scenario. If a human only comes into contact with the acid after it has been heavily diluted, the risk of harm will be minimal but the hazardous property of the chemical will remain unchanged.” Hence, the nature of hazard remains the same, but exposure dictates whether harm will actually occur.

11.2 Looking for answers Risk assessment is a process that results with understanding of risks, their causes, consequences, and their probabilities. Risk is always related to what might happen in the future [10]. Accordingly, it is characterised by some level of uncertainty. The purpose of risk assessment is to provide information so that well-informed decisions can be made. Basically, risk assessment looks for the answers to three main questions [14]: – What can happen? – What is the likelihood of that happening? – What are the consequences? Answer to the question “What can happen?” describes what could go wrong. It identifies scenario or hazardous event [10, 14]. The question can be answered in a number of ways and we have to identify all hazardous events that may cause harm. Hazardous event is defined [10] as the first event in a sequence of events that, if not controlled, will lead to the undesired consequences. Figure 11.1 illustrates a sequence of events that led to the spilled milk as an undesired consequence.

Figure 11.1: Illustration of hazardous event, sequence of events and undesired consequence.

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Answer to the second question describes how likely it is that a particular scenario or hazardous event actually happens. When describing the likelihood we can use qualitative statements or probabilities or frequencies [10]. When answering the third question we have to identify the adverse effects or consequences to human health, environment or material goods which can be expressed as some sort of cost [6]. Taking into account that both frequency/probability and the consequences refer to the specific hazardous event, i. e. scenario which is taking place, eq. (11.1) can be modified to eq. (11.2): Risk = f ðScenario, Frequency or Probability, ConsequencesÞ

(11:2)

representing the “set of triplets” idea proposed by Kaplan and Garrick [14]. Lindhe [15] gave an example of a “set of triplet” in analysing the risks in drinking water system, where scenario includes a pipe burst with estimated probability of 0.05 that may result with an interruption in the delivery of drinking water to 100 people for 8 hours period as a consequence. When the consequences of all identified scenarios are considered, the overall risk can be expressed by eq. (11.3) [15]: R = jfSi , pi , Xi gjc

(11:3)

whereas R stands for risk, S stands for scenario, p stands for probability and X for consequence, index i = 1,2, . . .. . . n indicates that there are more than one scenario and index c means complete risk.

11.3 Conceptual models Another question to be answered in risk assessment is: Who (or what) can be affected and how? It depends on our knowledge and belief how the real system in question behaves. One way to formalise this is to develop a conceptual model. Source–pathway–receptor concept (Figure 11.2) is often used in ERA. It can be easily correlated with the above discussed scenario.

SOURCE

PATHWAY

RECEPTOR

Figure 11.2: Concept source– pathway–receptor used in environmental risk assessment.

In this conceptual model the pathway between a hazard source and a receptor is investigated. The pathway is considered as the linkage by which the receptor could come into contact with the source. If no pathway exists then no risk exists [16].

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For a single source affecting the single receptor, the conceptual model might be simple. An example is given in Figure 11.3. It is a simplified representation of a risk of human exposure to the volatile toxic chemical transported from the source through the air.

Figure 11.3: Human exposed to volatile toxic chemical through the air path.

However, a number of pathways often need to be considered and conceptual models became more complex. Table 11.1 present examples of some of the possible sources, pathways and receptors [16]: Table 11.1: Examples of sources, pathways and receptors in environmental risk assessment. Source

Pathway

Receptor

Industrial emission Leaking pipelines Chemical release Contaminated soils Contaminated water

Water Air Soil Food chain

People Ecosystems Animals Plants Water supply

Conceptual model sets boundaries and components of the system and defines the relationships within. It is usually presented in narrative and graphical form. It should include sources and receptors, and exposure pathways. A chain of events must occur to result in exposure. The chain in a collective sense is termed an exposure pathway, the environmental routs which connect source site and receptor [17]. Hence, exposure pathway for a chemical includes chemical release mechanism, transport and transfer mechanism, possible transformation mechanisms, exposure point, and exposure routes. The example is given in Figure 11.4. The source (1) is a disposed barrel containing hazardous waste chemical. The receptors are residents (2) of the settlement near

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3

1

4

6

2 9

8

7 5

Figure 11.4: Conceptual model of waste disposal location.

disposal location. The chemical can be released by volatilisation and transported through the air (3) to the exposure point, whereas the inhalation by receptor (4) is considered as exposure route. The chemical can be also released by leaching (5) and transported by the ground water flow to the water table. Residential well (6) is considered as an exposure point, whereas the ingestion of contaminated water is exposure route for the residents consuming the potable water from the well. Another considered release mechanism is a spill of chemical (7) which is transported through the soil as a contaminated exposure medium. Spilled chemical can reach the water table through the soil. The chemical can be transferred from contaminated soil to the crops (8), whereas the crop ingestion is an exposure route for the residents. In the same manner animal grazing might be contaminated, and the consequent, indirect exposure route is ingestion of meat and milk (9). As it can be seen, there are more than one exposure pathways even in a case of above simple example. At the end of the risk assessment process, existing controls should be recorded and further measures may need to be considered to reduce or eliminate the risks identified. Detailed consideration of risk management is beyond the scope of this chapter but, in general terms, risk can be treated by reducing or modifying the source, by managing or breaking the pathway and/or modifying the receptor.

11.4 Risk assessment framework Risk assessment is a structured process set in the wider frame of risk management (Figure 11.5). Risk assessment generally comprises of three steps: (1) risk identification, (2) risk analysis and (3) risk evaluation, providing the input for risk treatment and the overall risk management process.

11.4 Risk assessment framework

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RISK ASSESSMENT risk identification risk analysis risk evaluation

RISK ASSESSMENT

Figure 11.5: Risk assessment frame and structure.

According to ISO Risk management – Vocabulary [18], risk is defined as effect of uncertainity on objectives. It should be noted that the objectives can have different aspects such as financial, health and safety, as well as environmental goals. Risk is often expressed in term of combination of the consequences of an event and the associated likelihood of occurrence. Risk identification [18] is a process of finding, recognising and describing the risk. It involves identification of risk sources, hazardous events, their causes and potential consequences. Risk analysis is defined as a process to comprehend the nature of risk and the level of risk. Risk analysis consists of determining consequences and their probabilities for identified scenarios, taking into account existence and effectiveness of control measures. Note that level of risk represents the magnitude of risk expressed in the terms of consequences and their likelihood. Hence, for level of risk eq. (11.1) applies with regard to hazardous event identified in previous step. The purpose of risk evaluation is to determine whether the risk is acceptable or tolerable and provides a base for decisions on how to deal with the undesired, negative consequences in risk treatment as a part of risk management process. IEC/ISO Risk management – Principles and guidelines standard [19] is intended for organisations of all types and sizes that seek to address uncertainties and increase the likelihood of achieving their objectives by adopting the effective risk management practice. However, the same principles and similar structure of risk assessment is applied within other fields such as environmental risk management. The objectives of risk assessment include [20] (i) protection of human and ecological health form adverse effects resulting from exposures to hazardous agents or situations (e. g. toxic substances), (ii) balance risks and benefits from usage hazardous substances such as drugs and pesticides, (iii) set target level of risk (e. g. food contaminants and water pollutants), (iv) set priorities from program activities to be used by regulatory agencies, manufacturers and environmental consumers organisations and (v) estimate residual risks and extent of risk reduction after steps are taken to reduce risks.

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11.5 Environmental risk assessment Risk assessment has become a commonly used approach in examining environmental problems mainly caused by human activities, [8, 13] whereas risks under consideration may be of very different natures. ERA [13] is the examination of risks resulting from technology that threaten ecosystems, animals and people, whereas the target/receptors as well as end-points are varied. Accordingly, and taking into account historical development as well as regulatory and policy imperatives and scope, a typology of risk assessment methods breaks ERA into: – Human health risk assessment – Ecological risk assessment – Applied industrial risk assessment ERA includes following steps: (1) problem formulation, (2) hazard identification, (3) release assessment, (4) exposure assessment, (5) consequence assessment and (6) risk estimation. Risk evaluation (7) is included in assessment of risks of existing and new chemicals that consider emission and the resulting exposure to the environment and humans in all life cycle steps. However, it may be included in other types of risk assessment. It should be noted that the political, economic, legal and social factors influence problem formulation as well as and risk evaluation, and consequently the decisions made within risk management. As it can be seen ERA steps fits well in above described general risk assessment structure (Figure 11.5). Namely, hazard identification is comprised in risk identification. Release assessment examines likelihood and the magnitude of the release, while exposure assessment examines the pathway and doses that receptor receives, revealing the source–pathway–receptor concept within ERA. Consequence analysis (or dose-response assessment) determines what is the effect on the receptor, while risk estimation gives a quantitative or qualitative measure of the risk. Hence, former steps can be clearly correlated with the risk analysis step within the general risk assessment structure. Risk assessment and management is used as decision making tool in: – the design of regulation; in determining societally acceptable risk levels as a base for environmental standards – providing the basis for site-specific decisions, in land-use planning or sitting of hazardous installations. – prioritisation of environmental risks; in determination of which chemicals to regulate first – comparison of the risks between different risk control measures and substitution decisions. Risk assessment enables the objective decision on whether risks posed by the chemical at certain dose outweigh the benefits of its use, i. e. whether risk is

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acceptable or not. The term “acceptable risk” might be ambiguous as it heavily depends on risk perception and the question “acceptable to whom” always arises. Risk perception [13] involves people’s beliefs and attitudes, judgments and feelings, as well as the wider social and cultural values that people adopt toward hazard and their benefits. Hence, risk perception will be a major determinant in whether a risk is deemed to be acceptable and whether the risk management measures are seen to resolve the problem. Risk management is the decision-making process through which choices can be made between a range of options which achieve the “required outcome” specified by environmental standards, determined by a formalised risk-cost-benefit analysis or “industry norms” or “good practice” [13]. Within the risk management process [19] risk can be treated by applying appropriate option(s) for changing the probability or the severity of the consequences related to the unacceptable risks. The residual or acceptable risks may be retained, [18] i. e. the potential benefit of gain, or burden of loss, from a particular risk may be accepted. One of definitions for acceptable risk given by Rausand [10] is: risk considered insignificant and not justifying further effort to reduce it. European Seveso directive [11] is an example of incorporation of risk assessment in regulation for site-specific problems. The Directive covers establishments where dangerous substances may be present in quantities above a certain threshold. The operators of industrial sites where dangerous substances are produced, used, handled or stored, or may be generated during loss of control of the process, are required to identify the potential major accident hazards and to provide the evidence that the adequate steps have been taken to prevent accidents and to limit the possible consequences to people and environment. Among number of activities used to categorize the Seveso establishments, seven activities contribute to 50 % of establishments: fuel storage (including heating, retail sale, etc.), wholesale and retail storage and distribution (excluding LPG-Liquefied petroleum gas), LPG storage, general chemicals manufacture, production of basic organic chemicals, power generation, supply and distribution, and LPG production, bottling and bulk distribution [21]. As risk assessment combines hazard and exposure data it enables prioritisation based on actual risk rather than the potential hazard [13]. Chemical risks are ranked on the basis of detailed information of risk effects, likelihood of exposure for different exposure scenarios priorities. However, it should be noted that the ability to provide detailed risk assessment is dependent on the availability of relevant toxicological data. Lack of complete data for numerous chemicals represents the limitation for the effective use of risk assessment in as an environmental management tool. Comparative risk is relative new field in European practice [13]. The aim is to ensure that the most severe risks are dealt with first, and that resources are devoted adequately with regard to the level of risk. Health risk assessment includes physical risks such as ionising radiation, biological such as pathogens or introduction of genetically modified organisms into

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the environment and the food chain, and chemical risks such as toxic substance. Different methodologies are applied for human health risk assessment depending on different toxic mechanisms exerted by different classes of chemical and the toxicological end-point being assessed [13]. The end-point being assessed could be death, or a specific pathological condition relating to exposure to a chemical. In some cases, such as immuno-suppressant toxins, specific end-points may be difficult to determine due to the role of other agents and stressors on the body. Hence, the methodology of risk assessment would differ from that applied for some other class of chemicals such as irritants. Ecological risk assessment [13] involves the assessment of the risks posed by the presence of substances released to the environment by man, on all living organisms in the variety of ecosystems which make up the environment. Methodology for ecological risk assessment is developed form human health assessment. Hence, the main difference between human health and ecological risk assessment can be seen in the scope of the process. Ecological risk assessment is characterised by the complex nature of the potential targets or receptors. Health risk assessment is concerned with individuals and morbidity and mortality, while ecological risk assessment is concerned with populations and communities and the effects of substances on mortality and fecundity. Ecological risk assessment has to deal with a multitude of organisms, all with varying sensitivities to chemicals and various groups have distinct exposure scenarios, such as free swimmers and sediment dwellers [13]. Because of the difficulty in obtaining toxicity data on all organisms in an ecosystem, the recognised practice is to test selected representatives of major taxonomic groups and use these as surrogates for the whole system. This method is questionable as it may not protect the most sensitive species exposed in the environment. Failure to identify the effects of an agent on a potential receptor can result in widespread damage to organisms and ecosystems. A typical example is the use of anti-fouling paints containing tributyltin and the resulting damaging effect on oysters and dog whelks [13]. Risk assessment methodology for industrial risk scenarios is a site specific and includes elements of either, or both, human health or ecological risk assessment [13].

11.6 Risk assessment methodology The methodologies for human health risk assessment for chemicals are mostly based on so-called NAS model developed by US National Academy of Sciences [22]. It includes: (1) hazard identification, (2) dose-response assessment, (3) exposure assessment and (4) risk estimation/characterisation, Figure 11.6. The methodology for human health and ecological risk assessment used in the regulation of new and existing substances in the EU [23] consists of the same steps used in above NAS model, although hazard identification and dose-response assessment are combined in the single step called Effects Assessment as presented in Figure 11.7.

11.6 Risk assessment methodology

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HAZARD IDENTIFICATION

DOSE-RESPONSE ASSESSMENT

EXPOSURE ASSESSMENT

RISK ESTIMATION/CHARACTERIZATION

Figure 11.6: Four step risk assessment process, NAS.

EFFECTS ASSESSMENT

EXPOSURE ASSESSMENT

RISK ESTIMATION/CHARACTERIZATION

Figure 11.7: Three step risk assessment process, EU.

Corresponding research activities are required for each step. Namely, for hazard identification within effect assessment, laboratory and fields observation of adverse health effects and exposures to particular agent are needed in order to determine does the agent cause the adverse effect. According to technical guidance on risk assessment [23] the risk assessment process, in relation to both human health and the environment, entails a sequence of actions as presented in Figure 11.7:

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1.

2.

3.

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Assessment of effects, comprising a. Hazard identification: identification of the adverse effects which a substance has an inherent capacity to cause; and b. dose (concentration)-response (effects) assessment: estimation of the relationship between dose, or level of exposure to a substance, and the incidence and severity of an effect, where appropriate. Exposure assessment: estimation of the concentrations/doses to which human populations (i. e. workers, consumers and man exposed indirectly via the environment) or environmental compartments (aquatic environment, terrestrial environment and air) are or may be exposed. Risk characterisation: estimation of the incidence and severity of the adverse effects likely to occur in a human population or environmental compartment due to actual or predicted exposure to a substance, and may include “risk estimation”, i. e. the quantification of that likelihood.

To improve the protection of human health and the environment from the risks that can be posed by chemicals, while enhancing the competitiveness of the EU chemicals industry, European Union adopted REACH regulation (Registration, Evaluation, Authorisation and Restriction of Chemicals) [24]. REACH applies to all chemical substances; not only those used in industrial processes but also in our day-to-day lives, for example in cleaning products, paints as well as in articles such as clothes, furniture and electrical appliances. REACH establishes procedures for collecting and assessing information on the properties and hazards of substances. A main task of REACH is to address data gaps regarding the properties and uses of industrial chemicals. Information sets to be prepared include safety data sheets (SDS), chemical safety reports (CSR), and chemical safety assessments (CSA). These are designed to guarantee adequate handling in the production chain, in transport and in use and to prevent the substances from being released to and distributed within the environment. Another important aim is to identify the most harmful chemicals and to set incentives to substitute them with safer alternatives [25].

11.7 Risk assessment for chemicals Any chemical which could potentially cause harm is considered to be hazardous. Certain chemicals can cause different types of harm, ranging from mild skin irritation to cancer. They can also have significant impacts on the environment, including the air, water and land; and they may adversely affect plants and animals. A chemical can only cause harm to our health or to the environment, if we are exposed to it [26]. The risk assessment for human health addresses the following potential toxic effects and human populations, considering each population’s exposure by the inhalation, oral and dermal routes [23]:

11.7 Risk assessment for chemicals

– – – – – – – –

369

Effects: acute toxicity; irritation; corrosivity; sensitisation; repeated dose toxicity; mutagenicity; carcinogenicity; toxicity for reproduction.

Human population: – workers; – consumers; – humans exposed indirectly via the environment. The information required for the technical dossier of chemical substance includes [23]: i. physiochemical properties such as state of the substance at 20 °C and 101,3 kPa, melting-point, boiling-point, relative density, vapour pressure, surface tension, water solubility, partition coefficient n/octanol/water, flash-point, flammability, explosive properties, self-ignition temperature, oxidizing properties, and granulometry;Data on physico-chemical properties are important for both the exposure assessment and the effects assessment. For example, physico-chemical properties are used to estimate emissions and the human exposure scenarios, to assess the design of toxicity tests, and may also provide indications about the absorption of the substance for various routes of exposure. ii. toxicological studies including: acute toxicity (administered orally, by inhalation and cutaneously, skin irritation, eye irritation and skin sensitisation), repeated dose whereas the route administration should be the most appropriate having regard to the likely route of human exposure, the acute toxicity and the nature of the substance, and other effects including mutagenicity, screening for toxicity related to reproduction and assessment of the toxicokinetic behaviour of a substance to the extent that can be derived from base set data and other relevant information. iii. ecotoxicological studies including effects on organisms such as acute toxicity for fish, acute toxicity for daphnia, growth-inhibition test on algae and bacterial inhibitor, degradation (biotic and abiotic, and hydrolysis as a function of pH for substances that are not readily biodegradable), adsorption/desorption screening tests. The principle of the assessment of chemical risks for human health is to compare the concentration of substance to which population is exposed with the concentration at which no adverse (toxic) effects are expected to occur [13, 23].

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No Observed Adverse Effect Level (NOAEL) is the outcome of the dose-response assessment. Where it is not possible to establish a NOAEL but a Lowest Observed Adverse Effect Level (LOAEL) can be derived, the latter is compared with the exposure level. The exposure levels can be derived based on available monitoring data and/or model calculations. Both NOAEL and LOAEL values are determined on the basis of results from animal testing, or on the basis of available human data. The risk characterization involves calculation of the exposure to effect ratio or a qualitative evaluation or the likelihood that an effect will occur at the give exposure. The risk reduction measures may include [13]: – providing information on the public regarding the safe and responsible handling of substances or products – the use of emission permits which set limits – marketing restrictions such as limiting production, import or use – total ban of a substance or activity The environmental risk assessment approach [27] address the concern for the potential impact of individual substances on the environment by examining both exposures resulting from discharges and/or releases of chemicals and the effects of such emissions on the structure and function of the ecosystem. Three approaches are used for this examination [27]: – quantitative estimation of Predicted Environmental Concentration (PEC) to Predicted No Effect Concentration (PNEC) ratio, i. e. quantitative PEC/PNEC estimation for ERA of a substance comparing compartmental concentrations with the concentration below which unacceptable effects on organisms will most likely not occur. This includes also an assessment of food chain accumulation and secondary poisoning; – the qualitative procedure for the ERA of a substance for those cases where a quantitative assessment of the exposure and/or effects is not possible; – the PBT assessment of a substance consisting of an identification of the potential of a substance to persist in the environment, accumulate in biota and be toxic combined with an evaluation of sources and major emissions, whereas PBT stands for Persistent, Bioaccumulative and Toxic. In principle, human beings as well as ecosystems in the aquatic, terrestrial and air compartment are to be protected. At present, the ERA methodology has been developed for the following compartments [27]: For inland risk assessment: – aquatic ecosystem (including sediment); – terrestrial ecosystem; – top predators; – microorganisms in sewage treatment systems; – atmosphere.

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– –

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For marine risk assessment: aquatic ecosystem (including sediment); top predators.

In addition to three primary environmental compartments, effects relevant to the food chain (secondary poisoning) are considered as well as effects on the microbiological activity of sewage treatment systems because proper functioning of sewage treatment plants is important for the protection of the aquatic environment. Different targets of the risk characterisation and the exposure scenarios, i. e. media of exposure for inland risk assessment and the marine environment as well as of indirect human exposure through the environment are presented in Table 11.2 [27].

Table 11.2: Relationship between different targets of the risk characterisation and medium of exposure. Target Inland compartments Aquatic organisms Benthic organisms Terrestrial organisms Fish-eating predators Worm-eating predators Microorganisms Marine compartment Aquatic organisms Benthic organisms Fish-eating predators Top predators Indirect human exposure Drinking water production Inhalation of air Production of crops Production of meat and milk Fish for human consumption

Media of exposure Surface water Sediment Aquatic soil Fish Earthworms Aeration tank (sewage treatment processes) Seawater Marine sediment Fish Fish-eaters Surface water, groundwater (annual average) Air (annual average) Agricultural soil (averaged over 180 days) Grassland (averaged over 180 days) Surface water (annual average)

Effects Assessment involves the identification of the hazard based on its physicochemical properties, ecotoxicity and intended use, and the estimation of a Predicted No Effect Concentration (PNEC), derived from ecotoxicity data and the application of assessment factors. Exposure assessment involves the calculation of a PEC. This is derived using monitoring data, realistic worst cases scenarios and predictive modelling techniques. It is a complex task and should consider release, degradation, and transport and fate mechanisms.

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Risk characterisation involves the calculation of a quotient – the PEC/PNEC ratio. If the ratio is less than 1 the substance is considered to present no risk to the environment in a given scenario. The Organisation for Economic Co-operation and Development (OECD) developed similar scheme and delivered a set of practical tools on ERA for chemicals [28]. Interactive OECD ERA toolkit describes the general work flow of ERA and provides links to relevant tools developed by OECD and member countries that can be used in each step of the work flow. The toolkit comprises five examples, provide a roadmap of the process, showing the steps involved in each case and the tools which were used on risk assessment. It includes a textile dye, pesticide and metal, end examples on setting an environmental quality standards, and initial screening of substances for persistent, bioaccumulative and toxic properties, as well and on compliance with limits set in a permit regarding ait pollution. Similarly, a toolkit on human health risk assessment for chemicals is developed by World Health Organisation (WHO) within the International Programme on Chemical Safety (IPCS) project on the Harmonization of approaches to assessment of risks from exposure to chemicals [29].

11.8 Dose–response relationship Effect assessment comprises of hazard identification and dose–response assessment. In human health risk assessment for chemicals hazard is described as [13] the identification of those substances that are deemed to be hazardous in some concentration or dose. Such assumption is based on physical chemical and toxicological properties of the chemical and on environmental fate mechanism. A fundamental principle in toxicology is that a relation exists between the dose of an agent (chemical) received and the response produced. Paracelsus (1493–1541), sometimes called father of toxicology, is frequently quoted for his saying [30, 31]: “What is there that is not poison? All things are poison and nothing (is) without poison; only the dose makes that a thing is no poison.” In short: “The dose makes the poison.” Paracelsus was the first one who recognised that dose is the most important in determining whether certain chemical is toxic or not. However, he did not have a quantitative notion on how much difference there was between the doses of a substance that separated a poison from a drug. Low doses of certain substances were found to be useful as curative while relatively high doses of the same substance were considered toxic [30]. The body’s response to the chemicals depended on the dose received. Consumption of small amounts wine and spirits is considered to be safe. Ethanol blood level of 0.05 % is considered non-toxic, while toxic and lethal dose are determined to be 0.1 % and 0.5 %, respectively [32]. Beneficial dose of aspirin is 2 tablets (0.65 g), while 30 and 105 tablets make toxic and lethal dose, respectively [32].

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Dose–response relationship is a relationship between exposure and health effect, which can be established by measuring the response relative to an increasing dose. The dose–response relationship is based on observed data from experimental animal, human clinical, or cell studies. Typical dose–response curve is presented in Figure 11.8.

100

Respons, %

A

B

0 Increasing dose → Figure 11.8: Dose–response curve for chemicals A and B.

Such dose–response curve establishes causality that the chemical has in fact induced the observed effects, indicates the lowest dose where an induced effect occurs, and determines the rate at which injury builds up (the slope for the dose response). The NOAEL (no observable adverse effect level) identified in a particular test will be simply the highest dose level or concentration of the substance used in that test at which no statistically significant adverse effects were observed, i. e. it is an operational value derived from a limited test [23]. For example if the dose levels of 200, 50, 10 and 5 mg/kg/day of a substance have been used in a test and adverse effects were observed at 200 and 50 mg/kg/day/but not at 10 or 5 mg/kg/day, the derived NOAEL will be 10 mg/kg/day. Thus, the NOAEL and LOAEL (lowest observable adverse effect level) values for a given study would depend on the experimental study design, i. e. the selection of dose levels and the spacing between doses. A threshold for toxic effects occurs at the point where the body’s ability to detoxify a xenobiotic or repair toxic injury has been exceeded. For most organs there is a reserve capacity so that loss of some organ function does not cause decreased performance. Humans and other living organisms often can tolerate some degree of exposure to various chemicals before they became toxic or cause ill effect [7]. Hence, many trace metals are toxic in high concentrations but essential in very low quantities. Threshold dosage is a dosage below which there is no increase in adverse effect above natural background rates. It should be noted that for some effects, such as genotoxicity there are no threshold dosage.

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11 Risk assessment

Conservative assumption of zero thresholds is commonly used for carcinogens, while nonzero threshold is employed for other types of health effect [7]. The intersection of dose–response curve with the x-axis in Figure 11.7 indicates the threshold dosage. Below that level there is no observable adverse effect. Knowledge of the shape and slope of the dose–response curve is extremely important in predicting the toxicity of a substance at specific dose levels. Major differences among toxicants may exist not only in the point at which the threshold is reached but also in the percent of population responding per unit change in dose (i. e. the slope). As illustrated in Figure 11.8, toxicant A has a higher threshold but a steeper slope than toxicant B. Some of the common measures of observed effects include [12]: LC50: median lethal concentration LD50: median lethal dose EC50: median effective concentration LC10: lethal concentration to 10 % of test organisms where L stands for lethal, E stands for effective, C is concentration and D is dose. LD50 represents a dose of toxicant at which 50 % of tested organisms die within the specified time. EC50 is concentration at which 50 % of tested organisms exhibit the effect of exposure. Different sublethal effects can be examined such as percentage of organisms that fail to produce eggs or achieve specific height. For example Vibrio fischeri luminescence assays are often used as environmental monitoring tool for toxicity of environmental samples. Test is based on measuring changes in the light emitted by luminescent bacteria Vibrio fischeri upon exposure to medium containing toxic substance. Resulting EC50 is the effective concentration of a sample that causes a 50 % decrease in the light output of the test organisms under controlled conditions. The result is reported in the terms of IC50 which stands for inhibitory concentration measuring the quantitative reduction of light production relative to control. LC10 is lower than LC50 for the same organisms. EC50 is lower than LC50 as it measure effect other than lethal. Hence, toxic effects as a function of concentration follow increasing order: NOEC